Separator for Lithium Ion Battery

ABSTRACT

There is provided a method for producing a separator for an electricity storage device that includes a step of contacting a porous body formed from a silane-modified polyolefin-containing molded sheet with a base solution or acid solution, and a separator for an electricity storage device comprising a microporous film with a melted film rupture temperature of 180° C. to 220° C. as measured by thermomechanical analysis (TMA).

FIELD

The present invention relates to a separator for an electricity storagedevice and a method for producing it, and more specifically it relatesto a modified polyolefin-containing a microporous membrane that can besuitably used as a separator for a lithium ion battery, and to a methodfor producing it.

BACKGROUND

Microporous membranes are widely used as membranes for separation orselective permeation and selection of various substances and asisolating materials, and some examples of their uses include asmicrofiltration membranes, as fuel cell and condenser separators, or asmatrices for functional membranes or battery separators, which exhibitnew functions by having functional materials packed into their pores.Polyolefin microporous membranes, specifically, are preferred for use asseparators for lithium ion batteries that are widely utilized in PClaptops, cellular phones and digital cameras. In order to ensure batterysafety, separators must have both an active shutdown function and highmembrane rupture temperature. PTL 1, for example, describes adjustmentof the higher physical properties of a polyolefin resin as an essentialcomponent of a separator for a lithium ion battery. In addition, asdescribed in PTL 2, it is known that heat release due to interiorbattery short circuiting is inhibited by a shutdown function when thedegree of crystallinity and gel fraction are in specific ranges, andthat the safety of a battery can be ensured if it has performance suchthat a membrane rupture will not occur in the battery cell at partialhigh temperature sections (i.e. breakdown at 170° C. or higher). Morespecifically, in regard to PTLs 1 and 2, it has gradually come to lightby experimentation that high-temperature membrane rupture properties canbe exhibited by constructing silane crosslinked sections (a gelstructure) in a polyolefin separator.

CITATION LIST Patent Literature

-   [PTL 1] Japanese Unexamined Patent Publication No. H09(1997)-216964-   [PTL 2] International Patent Publication No. WO97/44839-   [PTL 3] Japanese Unexamined Patent Publication No. H11(1999)-144700-   [PTL 4] Japanese Unexamined Patent Publication No. H11(1999)-172036-   [PTL 5] Japanese Unexamined Patent Publication No. 2001-176484-   [PTL 6] Japanese Unexamined Patent Publication No. 2000-319441-   [PTL 7] Japanese Unexamined Patent Publication No. 2017-203145-   [PTL 8] International Patent Publication No. WO2010/134585-   [PTL 9] Japanese Unexamined Patent Publication No. 2016-072150-   [PTL 10] Japanese Unexamined Patent Publication No. 2007-299612

SUMMARY Technical Problem

With the increasing high outputs and high energy densities of lithiumion secondary batteries for mobile devices and vehicles in recent years,there is ongoing demand for smaller battery cell sizes and for stablecycle charge-discharge performance during long periods of use. It istherefore considered necessary for the separators used to bethin-membranes (for example, 15 μm or smaller) with high quality (forexample, homogeneous physical properties and free of resin aggregates).Standards have also become more rigorous for battery safety in additionto the performance mentioned above, and as also described in PTLs 1 and2, there is a need for shutdown functions and high-temperature membranerupture properties, while expectations are also high for development ofseparator resin compositions that can be stably produced, and productionmethods for them. In this regard, the level for shutdown temperature ispreferably as far below 150° C. as possible, while the membrane rupturetemperature is preferably as high a temperature as possible.

In the method described in PTL 3, for example, a crosslinking catalystmaster batch is used during the extrusion step to promotesilane-modified polyethylene crosslinking reaction in the extruder, butthis results in generation of resin aggregates and lowers thehomogeneity of the physical properties of the separator. As a solutionfor this problem, the methods described in PTLs 4, 5 and 6 proposeproviding a plasticizer extraction step or silane gel crosslinking step,or controlling the gel fraction of the resin membrane, or dewateringafter casting of the uncrosslinked resin through hot water. In addition,PTL 7 proposes a polyolefin microporous membrane with modification ofthe gel fraction, storage elastic modulus, maximum shrinkage factorbased on thermomechanical analysis (TMA) and amount of radicals asmeasured by electron spin resonance (ESR), to provide a heat-resistantresin microporous membrane with low heat shrinkage, low fluidity andexcellent meltdown resistance.

In addition, from the viewpoint of dimensional stability, and of bothmaintaining the shutdown function and increasing the membrane rupturetemperature for separators for electricity storage devices, it has beenproposed to provide an inorganic porous layer containing inorganicparticles such as calcined kaolin or boehmite and a resin binder on atleast one surface of a polyolefin microporous membrane (PTLs 8 and 9). Aseparator has also been proposed that has a layer A having a shutdownproperty and a layer B comprising an aramid resin and an inorganicmaterial, with the ratio of their thicknesses adjusted to within aprescribed range (PTL 10).

However, the method disclosed in PTL 4 is not able to sufficientlypromote silane crosslinking reaction, and it is difficult to obtainhigh-temperature membrane rupture resistance. Crosslinking reaction canbe promoted in the plasticizer extraction steps described in PTLs 3 and4 since they employ a tin(II)-based crosslinking catalyst, but there areconcerns regarding post-residue of the crosslinking catalyst.

The heat-resistant resin microporous membrane described in PTL 7 ismerely obtained by coating a photopolymerizable coating solution onto adry porous membrane. In Example 5 of PTL 7 a low-molecular-weight silanecoupling agent such as γ-methacryloxypropyltrimethoxysilane is added tothe porous membrane, but when a low-molecular-weight silane couplingagent is used in a wet porous method, it is expected that thelow-molecular-weight silane coupling agent does not bond with the resinof the porous membrane since it tends to react or bond with thepore-forming plasticizer.

Moreover, the film layer described in PTL 7 is formed by coating acompound with a polymerizable functional group onto a resin porousmembrane followed by crosslinking reaction by external stimulation, andtherefore some infiltration into the resin porous membrane is expectedto occur during coating of the film layer, and a mixed region isexpected to form near the interface between the film layer and the resinporous membrane after the crosslinking reaction has proceeded. Thisallows satisfactory TMA heat shrinkage performance to be obtained, butis also expected to lead to lower battery cycle characteristics due toblockage of the resin porous membrane, or reduced fuse (shutdown)performance as the resin porous membrane undergoes melting. In addition,small amounts of radical species compounds are detected by ESR andremain in the composite microporous membrane obtained by the methoddescribed in PTL 7, and when such a composite microporous membrane hasbeen incorporated into a battery, radical reaction would be expected totake place with the other members and particularly the electrolytesolution, resulting in chain reaction that would decompose theelectrolyte solution, thus potentially resulting in notable impairmentof the battery performance.

A battery using a separator such as described in PTLs 3 to 7 has poorcycle characteristics, and when used for prolonged periods unpredictablesecondary reactions may be induced in the battery, potentially loweringthe battery safety. While silane crosslinking is problematic forobtaining a shutdown function and high-temperature membrane ruptureproperties as explained above, the porous body structure, which is themost important aspect of the separator, cannot be constructed with asilane-grafted polyolefin alone, and therefore the development of resinmixture compositions is also essential.

Furthermore, the microporous membranes and separators described in PTLs1, 2 and 7 have been poorly studied in terms of placing inorganic porouslayers comprising inorganic particles and a resin binder on theirsurfaces. A conventional separator comprising an inorganic porous layeron a microporous membrane will appear to have an improved membranerupture temperature in the temperature-resistance curve of anelectricity storage device. In practice, however, since the resin oftenelutes from the microporous membrane into the inorganic porous layer,loss of the membrane and a resulting reduction in stress resistance areto be expected for the separator as a whole. The multilayer porousmembranes described in PTLs 8 and 9 are therefore provided with apolyolefin microporous membrane and an inorganic porous layer, but thereis still room for investigation regarding both the low temperatureshutdown function and high-temperature membrane rupture properties as aseparator for an electricity storage device, and regarding improvedelectricity storage device cycle characteristics and battery nailpenetration safety.

With the separators for electricity storage devices described in PTLs 1,2 and 10, there is still room for improvement from the viewpoint ofimproving their electricity storage device performance.

In light of these problems, it is an object of the present invention toprovide a separator that has both a shutdown function andhigh-temperature membrane rupture properties, and that can improve theelectricity storage device output, cycle characteristic and/or safety,as well as a method for producing it.

Solution to Problem

As a result of much avid research directed toward solving theseproblems, the present inventors have completed this invention uponfinding that they can be solved if crosslinking reaction (gelation) iscarried out under specific conditions after completion of a step inwhich the higher-order structure of the microporous membrane isconstructed using a resin composition with a specific resin composition.

Specifically, the present invention provides the following.

[1]

A method for producing a separator for an electricity storage device,comprising the following steps:

(1) a sheet-forming step in which a silane graft-modified polyolefin,polyethylene and a plasticizer are extruded into a sheet using anextruder, cooled to solidification and shaped into a molded sheet;

(2) a stretching step in which the molded sheet is subjected to biaxialstretching to a 20-fold to 250-fold area increase to form a stretchedsheet;

(3) a porous body-forming step in which the plasticizer is extractedfrom the stretched sheet to form a porous body;

(4) a heat treatment step in which the porous body is subjected to heattreatment and subjected to stretching and relaxation in the transversedirection to obtain a heat-treated porous body;

(5) an affinity treatment step in which the heat-treated porous body isimmersed in an organic solvent that is amphiphilic for water and organicmaterials, and the liquid affinity of the heat-treated porous body isincreased to obtain an affinity-treated porous body impregnated with theorganic solvent;

(6) a crosslinking step in which the affinity-treated porous body iscontacted with a mixture of an organometallic catalyst and water, or isimmersed in a base solution or an acid solution and subjected to silanedehydration condensation reaction to form oligosiloxane bonds, obtaininga crosslinked porous body; and

(7) a washing and drying step in which the crosslinked porous body iswashed with water and dried.

[2]

The method for producing a separator for an electricity storage deviceaccording to [1] above, wherein the weight ratio of the silanegraft-modified polyolefin and the polyethylene (silane graft-modifiedpolyolefin weight/polyethylene weight) is 0.05/0.95 to 0.40/0.60.

[3]

The method for producing a separator for an electricity storage deviceaccording to [1] or [2] above, wherein the separator for an electricitystorage device comprises a microporous membrane having a melted membranerupture temperature of 180° C. to 220° C. as measured bythermomechanical analysis (TMA).

[4]

The method for producing a separator for an electricity storage deviceaccording to any one of [1] to [3] above, wherein in the crosslinkingstep, the affinity-treated porous body is immersed in the base solutionor acid solution.

[5]

The method for producing a separator for an electricity storage deviceaccording to [4] above, wherein in the crosslinking step, theaffinity-treated porous body is immersed in the base solution.

[6]

The method for producing a separator for an electricity storage deviceaccording to [5] above, wherein the temperature of the base solution is20° C. to 100° C. and the pH thereof is 8 to 14.

[7]

The method for producing a separator for an electricity storage deviceaccording to [4] above, wherein in the crosslinking step, theaffinity-treated porous body is immersed in the acid solution.

[8]

The method for producing a separator for an electricity storage deviceaccording to any one of [1] to [7] above, wherein the metal of theorganometallic catalyst is one or more selected from the groupconsisting of scandium, vanadium, copper, zinc, zirconium, palladium,gallium, tin, titanium, iron, nickel and lead.

[9]

The method for producing a separator for an electricity storage deviceaccording to any one of [1] to [8] above, wherein the content of thescandium, vanadium, copper, zinc, zirconium, palladium, gallium, tin,titanium, iron, nickel or lead in the separator for an electricitystorage device is 0.10 ppm to 200 ppm as the total in terms of atoms.

[10]

The method for producing a separator for an electricity storage deviceaccording to any one of [1] to [9] above, wherein the silanegraft-modified polyolefin is not a master batch resin containing adehydrating condensation catalyst that crosslinks the silanegraft-modified polyolefin before the sheet-forming step.

[11]

The method for producing a separator for an electricity storage deviceaccording to any one of [1] to [10] above, wherein in the washing anddrying step, the crosslinked porous body is washed with water at atemperature of 20 to 100° C. and a pH of 6 to 8 and dried.

[12]

A method for producing an electricity storage device, comprising thefollowing steps:

a step of laminating and/or winding a positive electrode, a separatorfor an electricity storage device obtained by the method for producing aseparator for an electricity storage device according to any one of [1]to [11] above, and a negative electrode, to obtain a laminated stack orwound body;

a step of inserting the laminated stack or wound body into an exteriorbody;

a step of pouring an electrolyte solution into the exterior body; and

a step of connecting lead terminals to the positive electrode andnegative electrode.

[13]

The method for producing an electricity storage device according to [12]above, wherein the electrolyte solution includes a LiPF₆-containingelectrolyte or another fluorine (F)-containing lithium salt electrolyte.

[14]

A separator for an electricity storage device that comprises amicroporous membrane including a silane-modified polyolefin andpolyethylene, wherein the melted membrane rupture temperature of themicroporous membrane is 180° C. to 220° C. as measured bythermomechanical analysis (TMA).

[15]

The separator for an electricity storage device according to [14] above,wherein the separator for an electricity storage device includesscandium, vanadium, copper, zinc, zirconium, palladium, gallium, tin,titanium, iron, nickel or lead at 0.10 ppm to 200 ppm as the total interms of atoms.

[16]

The separator for an electricity storage device according to [14] or[15] above, wherein the separator for an electricity storage deviceincludes zinc or tin at 0.10 ppm to 200 ppm as the total in terms ofatoms.

[17]

The separator for an electricity storage device according to any one of[14] to [16] above, which comprises:

the microporous membrane and

an inorganic porous layer that includes inorganic particles and a resinbinder, disposed on at least one surface of the microporous membrane.

[18]

The separator for an electricity storage device according to [17] above,wherein the content of the inorganic particles in the inorganic porouslayer is 5 weight % to 99 weight %.

[19]

The separator for an electricity storage device according to [17] or[18] above, wherein the content of the silane-modified polyolefin in themicroporous membrane is 0.5 weight % to 40 weight %.

[20]

The separator for an electricity storage device according to any one of[17] to [19] above, wherein the inorganic particles are one or moreselected from the group consisting of alumina (Al₂O₃), silica, titania,zirconia, magnesia, ceria, yttria, zinc oxide, iron oxide, siliconnitride, titanium nitride, boron nitride, silicon carbide, aluminumhydroxide oxide (AlO(OH)), talc, kaolinite, dickite, nacrite,halloysite, pyrophyllite, montmorillonite, sericite, mica, amesite,bentonite, asbestos, zeolite, diatomaceous earth, quartz sand and glassfibers.

[21]

The separator for an electricity storage device according to any one of[17] to [20] above, wherein the glass transition temperature (Tg) of theresin binder is −50° C. to 100° C.

[22]

A separator for an electricity storage device comprising a first porouslayer (layer A) with a crosslinked structure that includes asilane-modified polyolefin, and a second porous layer (layer B) thatincludes inorganic particles, wherein:

the ratio of the thickness (TA) of layer A with respect to the thickness(TB) of layer B (TA/TB) is 0.22 to 14.

[23]

The separator for an electricity storage device according to [22] above,wherein the membrane rupture temperature of layer A is 180° C. to 220°C., as measured by thermomechanical analysis (TMA).

[24]

The separator for an electricity storage device according to [22] or[23], wherein the total thickness of layer A and layer B (TA+TB) is 3.0μm to 22 μm.

[25]

The separator for an electricity storage device according to any one of[22] to [24], wherein the amount of the inorganic particles in layer Bis 20 weight % to 99.5% weight % based on the total weight of layer B.

[26]

The separator for an electricity storage device according to any one of[22] to [25], wherein layer B includes a resin binder.

[27]

The separator for an electricity storage device according to any one of[22] to [26], wherein layer A further includes polyethylene as apolyolefin different from the silane-modified polyolefin.

[28]

The separator for an electricity storage device according to any one of[22] to [27], wherein the amount of the silane-modified polyolefin inlayer A is 3 weight % or greater based on the total weight of layer A.

[29]

A separator for an electricity storage device wherein the shutdowntemperature is 130° C. to 160° C. and the meltdown temperature is 200°C. or higher, as measured based on the electrical resistance underpressure of 10.0 MPa.

[30]

A method for producing the separator for an electricity storage deviceaccording to any one of [14] to [29] above, comprising the followingsteps:

(1) a sheet-forming step in which a silane-modified polyolefin,polyethylene and a plasticizer are extruded into a sheet using anextruder, cooled to solidification and shaped into a molded sheet;

(2) a stretching step in which the molded sheet is subjected to biaxialstretching to a 20-fold to 250-fold area increase to form a stretchedsheet;

(3) a porous body-forming step in which the plasticizer is extractedfrom the stretched sheet to form a porous body;

(4) a heat treatment step in which the porous body is subjected to heattreatment and subjected to stretching and relaxation in the transversedirection to obtain a heat-treated porous body;

(5) an affinity treatment step in which the heat-treated porous body isimmersed in an organic solvent that is amphiphilic for water and organicmaterials, and the liquid affinity of the heat-treated porous body isincreased to obtain an affinity-treated porous body impregnated with theorganic solvent;

(6) a crosslinking step in which the affinity-treated porous body iscontacted with a mixture of an organometallic catalyst and water, or isimmersed in a base solution or an acid solution and subjected to silanedehydration condensation reaction to form oligosiloxane bonds, obtaininga crosslinked porous body;

(7) a washing and drying step in which the crosslinked porous body iswashed with water and dried to obtain a microporous membrane comprisingthe silane-modified polyolefin; and

(8A) a coating step in which an inorganic porous layer includinginorganic particles and a resin binder is formed on at least one surfaceof the microporous membrane.

[31]

An electricity storage device comprising an electrode, the separator foran electricity storage device according to any one of [14] to [29]above, and a nonaqueous electrolyte solution.

Advantageous Effects of Invention

According to the invention it is possible to provide both a shutdownfunction and high-temperature membrane rupture properties for aseparator for an electricity storage device, and to improve the output,cycle characteristic and/or safety of the electricity storage device,and/or to inhibit generation of unmelted resin aggregates during theproduction process for the separator for an electricity storage deviceor to ensure high-temperature, high-pressure resistance.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a TMA graph for the separator obtained in Example I-1.

FIG. 2 is a heat release graph for a nail penetration safety test for abattery using the separator obtained in Example I-1.

FIG. 3 is a voltage reduction graph for a nail penetration safety testfor a battery using the separator obtained in Example I-1.

FIG. 4 is an ¹H-NMR chart (a) and ¹³C-NMR chart (b) for silane-modifiedpolyolefin starting material 1 obtained using a polyolefin.

FIG. 5 is an ¹H-NMR chart (a) and ¹³C-NMR chart (b) for silane-modifiedpolyolefin starting material 2 obtained using a polyolefin.

FIG. 6 is an ¹H-NMR chart (a) and ¹³C-NMR chart (b) for the separatorfabricated using silane-modified polyolefin starting material 1, shownin FIG. 4 , in the state before crosslinking.

DESCRIPTION OF EMBODIMENTS

Embodiments of the invention will now be explained. The presentinvention is not limited only to the following embodiments and mayincorporate various modifications such as are within the scope of itsgist.

Throughout the present specification, the “to” in a numerical rangemeans that the numerical values on either side are included as the upperlimit and lower limit. The upper limits and lower limits for thenumerical ranges throughout the present specification may be combined asdesired. For example, the upper limit of a preferred numerical range maybe combined with the lower limit of a more preferred numerical range, orconversely, the upper limit of a more preferred numerical range may becombined with the lower limit of a preferred numerical range.

Throughout the present specification, “above”, “upper” and “formed on asurface” do not mean that the positional relationship of the respectivemembers is “directly above”. For example, the expressions “layer Bformed on layer A” and “layer B formed on the surface of layer A” do notexclude the case where an arbitrary layer not qualifying as either isincluded between layer A and layer B.

The properties of the microporous membrane alone that are describedbelow may be measured after removing layers other than the microporousmembrane (for example, an inorganic porous layer) from the separator foran electricity storage device.

<Separator for Electricity Storage Device>

One aspect of the invention is a separator for an electricity storagedevice (hereunder also referred to simply as “separator”). Theseparator, which must have an insulating property and ion permeability,will usually comprise an insulating material sheet with a porous bodystructure, a polyolefin nonwoven fabric or a resin microporous membrane.Particularly suited for a lithium ion battery is a polyolefinmicroporous membrane that allows construction of a compact homogeneousporous body structure with redox degradation resistance of theseparator.

A microporous membrane is a membrane composed of a porous body, and itsmean pore size is preferably 10 nm to 500 nm and more preferably 30 nmto 100 nm.

When the separator is included in an electricity storage device, theseparator is removable from the electricity storage device.

First Embodiment

The separator according to a first embodiment of the invention comprisesa microporous membrane wherein the melted membrane rupture temperatureis 180° C. to 220° C. as measured by thermomechanical analysis (TMA),and the microporous membrane includes a silane-modified polyolefin andsilane-unmodified polyethylene. From the viewpoint of high-temperaturemembrane rupture resistance and electricity storage device safety, themelted membrane rupture temperature of the microporous membrane is 180°C. to 220° C. and preferably 180° C. to 200° C., as measured bythermomechanical analysis (TMA). Even when the electricity storagedevice has generated abnormal heat release due to runaway reaction, theshutdown function of the separator is expected to stop movement of ions,and discharge in the electricity storage device or outside of theelectricity storage device that results from it. It is expected that theelectricity storage device as a whole is then cooled by a coolant, thusensuring the safety. On the other hand, if the membrane rupturetemperature of the microporous membrane is within the numerical rangespecified above, then the separator will undergo molten rupture and seeponto both electrodes so that the active materials can be coated, thuseven more easily inhibiting heat release even when the electricitystorage device as a whole is not sufficiently cooled, or even if anultra-high temperature range is reached. The membrane rupturetemperature of the microporous membrane can be measured by the methoddescribed in the Examples, and it can be controlled by changing thestretching temperature and/or stretch ratio during the productionprocess.

From the viewpoint of the production process and of controlling theamorphous part of the microporous membrane to ensure safety, theseparator of the first embodiment preferably has the content ofscandium, vanadium, copper, zinc, zirconium, palladium, gallium, tin,titanium, iron, nickel or lead controlled to within a range of 0.10 ppmto 200 ppm as the total in terms of atoms, more preferably it has thecontent of zinc or tin controlled to within the range of 0.10 ppm to 200ppm as the total in terms of atoms, and even more preferably it hastheir content controlled to within the range of 1 ppm to 150 ppm.

From the viewpoint of both a shutdown function at relatively lowtemperature and membrane rupture properties at relatively hightemperature, as well as improved cycle characteristics and safety of theelectricity storage device, the separator of the first embodiment mayalso comprise a microporous membrane; and an inorganic porous layerincluding inorganic particles and a resin binder, disposed on at leastone surface of the microporous membrane. The separator may also employthe microporous membrane as a base material, and may consist of acomposite of the base material and an inorganic coating layer.

Second Embodiment

The separator according to a second embodiment of the inventioncomprises a first porous layer (layer A) that has a crosslinkedstructure and includes a silane-modified polyolefin, and a second porouslayer (layer B) that includes inorganic particles. Layer A and layer Bare both either single layers or multiple layers. Layer B is formed ononly one side or on both sides of layer A.

In a LIB, as a typical electricity storage device, lithium (Li) ionsreciprocate between positive and negative electrodes. By situating aseparator comprising layer A and layer B between the positive andnegative electrodes, therefore, it is possible to cause relatively rapidmovement of Li ions between the positive and negative electrodes, whileavoiding contact between the positive and negative electrodes.

(Thickness Ratio)

Layer A functions as a crosslinkable microporous membrane, while layer Bfunctions as an inorganic porous layer to be formed on the microporousmembrane.

The ratio of the thickness (TA) of layer A with respect to the thickness(TB) of layer B (TA/TB) is 0.22 to 14. If the ratio (TA/TB) is 0.22 orgreater it will be possible to adequately ensure the presence of layer Ain the separator and to thus exhibit the function of layer A. If theratio (TA/TB) is 14 or lower, it will be possible to adequately ensurethe presence of layer B in the separator and to thus exhibit thefunction of layer B.

By forming layer A and layer B with their respective specific structuresand setting the ratio (TA/TB) to be within this range, it is possible toprovide a separator that can improve cycle characteristics and safety inan electricity storage device. The separator can be suitably used as aconstituent material of a LIB for mounting in a mobile device or avehicle.

From the viewpoint of this effect, the ratio (TA/TB) is preferably 0.8or greater and more preferably 1.0 or greater. The ratio (TA/TB) is alsopreferably no higher than 5.5 and more preferably no higher than 3.2.

The ratio (TA/TB) may be set to be lower than 2.5, 2.0 or lower, or 1.0or lower, for example. In this case, the thickness (TA) of layer A isless than 2.5 times the thickness (TB) of layer B, or even smaller thanthe thickness (TB) of layer B, thus allowing the layer A to be providedas a thinner membrane so that the separator thickness can be reduced.

The total thickness of layer A and layer B (TA+TB) is preferably 3.0 μmto 22 μm. If the total thickness (TA+TB) is 3.0 μm or greater themembrane strength of the separator will tend to be increased. If thetotal thickness (TA+TB) is 22 μm or smaller, on the other hand, the ionpermeability of the separator will tend to be increased.

From the viewpoint of this effect, the total thickness (TA+TB) is morepreferably 3.5 μm or greater and even more preferably 4.0 μm or greater.The total thickness (TA+TB) is also more preferably no greater than 20μm and even more preferably no greater than 18 μm.

The total thickness (TA+TB) may be set to less than 11 μm, 10 μm orsmaller or 8 μm or smaller, for example. Even with such a thin separatorit is still possible to improve the cycle characteristics and safety ofan electricity storage device, so long as the ranges of the inventionare satisfied.

The ratio (TA/TB) and the total thickness (TA+TB) may each be measuredby the methods described in the Examples, and they can be controlled byadjusting the thickness (TA) and/or the thickness (TB). Layer A andlayer B will now be described.

(Shutdown Temperature and Meltdown Temperature)

Layer A preferably has a shutdown temperature (also referred to as thefuse temperature) of 130° C. to 160° C. and a meltdown temperature (alsoreferred to as the membrane rupture temperature) of 200° C. or higher,as measured based on the electrical resistance under pressure of 0.1 MPato 10.0 MPa (preferably under pressure of 10 MPa).

If the shutdown temperature is 130° C. or higher it will be possible toavoid unnecessary operation of the shutdown function during periods ofnormal reaction in the electricity storage device, and the electricitystorage device can be ensured to have sufficient output characteristics.If the shutdown temperature is 160° C. or lower, on the other hand, theshutdown function can be suitably exhibited during periods of abnormalreaction in the electricity storage device.

In addition, a meltdown temperature of 200° C. or higher will be able tostop abnormal reaction before the ultra-high temperature range isreached during periods of abnormal reaction in the electricity storagedevice, and can prevent melting membrane rupture of the separator duringperiods of abnormal reaction of the electricity storage device.

In other words, if the shutdown temperature and meltdown temperaturesatisfy the conditions specified above, then it will be possible toobtain a separator that is able to provide an electricity storage devicewhich is excellent in terms of heat resistance, pore occlusion property(shutdown function) and melting membrane rupture property (meltdownfunction), and to ensure the mechanical properties and ion permeabilityof the separator itself. With a separator whose shutdown temperature andmeltdown temperature satisfy the aforementioned conditions, therefore,the electricity storage device can be designed with improved cyclecharacteristics and safety.

From the viewpoint of this effect, the shutdown temperature ispreferably higher than 130° C., more preferably 135° C. or higher andeven more preferably 136° C. or higher. The shutdown temperature is alsopreferably no higher than 150° C., more preferably no higher than 148°C. and even more preferably no higher than 146° C.

From the same viewpoint of this effect, the meltdown temperature ispreferably 175° C. or higher, more preferably 178° C. or higher and evenmore preferably 180° C. or higher. The meltdown temperature is alsopreferably no higher than 230° C., more preferably no higher than 225°C. and even more preferably no higher than 220° C.

The condition of “a meltdown temperature of 200° C. or higher” issatisfied even when the meltdown temperature cannot be accuratelymeasured in the range exceeding 200° C., so long as the temperature is200° C. or higher.

The terms “shutdown temperature” and “meltdown temperature” as usedherein are the values obtained upon measurement based on the electricalresistance under the pressure specified above. Specifically, theshutdown temperature and meltdown temperature are derived from thealternating-current resistance (alternating-current resistance betweenelectrodes) that increases with increasing temperature of the laminatedstack comprising the positive electrode, separator and negativeelectrode while applying the aforementioned pressure to the laminatedstack. For the second embodiment, the shutdown temperature is thetemperature at which the alternating-current resistance first exceeds aprescribed reference value (for example, 1000Ω), and the meltdowntemperature is the temperature at which the alternating-currentresistance exceeding the reference value falls below the reference value(for example, 1000Ω) as further heating is continued thereafter.

A hydraulic jack may be used for pressurizing of the laminated stack,but this is not restrictive, and any known pressurizing means other thana hydraulic jack may be used. An aluminum heater may be used for heatingof the laminated stack, but this is also not restrictive, and any knownheating means other than an aluminum heater may be used.

The shutdown temperature and meltdown temperature may be measured by themethods described in the Examples, and they can be controlled byadjusting the structure of and production method for layer A.

(Heat Shrinkage Factor at 150° C.)

The heat shrinkage factor (T2) at 150° C. after formation of thecrosslinked structure in layer A is preferably 0.02 to 0.91 times theheat shrinkage factor (T1) at 150° C. before formation of thecrosslinked structure. In other words, the ratio of the heat shrinkagefactor (T2) at 150° C. after formation of the crosslinked structure inlayer A with respect to the heat shrinkage factor (T1) at 150° C. beforeformation of the crosslinked structure (T2/T1) is preferably 0.02 to0.91. The heat shrinkage factor used here is the larger value of theheat shrinkage factor in the machine direction (MD) of layer A and theheat shrinkage factor in the transverse direction (TD) of layer A.

It is because layer A is able to form a crosslinked structure with asilane-modified polyolefin, that it is possible to notice a change inheat shrinkage factor before and after crosslinking.

If the ratio (T2/T1) is 0.02 or greater it will be possible toeffectively inhibit short circuiting, thereby reliably preventingtemperature increase of the electricity storage device as a whole andconsequent generation of fumes or ignition. It may be judged thatcrosslinking reaction in layer A has proceeded sufficiently if the ratio(T2/T1) is no greater than 0.91. That is, if the ratio (T2/T1) is withinthe range specified above, a separator for an electricity storage devicecan be provided that improves the cycle characteristics and safety foran electricity storage device.

From the viewpoint of this effect, the ratio (T2/T1) is preferably 0.03or greater, more preferably 0.05 or greater and even more preferably0.07 or greater. The ratio (T2/T1) is also preferably no greater than0.7, more preferably no greater than 0.5 and even more preferably nogreater than 0.4.

The heat shrinkage factor (T1) at 150° C. before formation of thecrosslinked structure is preferably no higher than 70% and morepreferably no higher than 60%.

The heat shrinkage factor (T2) at 150° C. after formation of thecrosslinked structure is preferably no higher than 60% and morepreferably no higher than 50%. Since formation of a crosslinkedstructure tends to result in a lower heat shrinkage factor compared tobefore formation of the crosslinked structure, the heat shrinkage factor(T2) will generally be a smaller value than the heat shrinkage factor(T1).

The heat shrinkage factor at 150° C. can be measured by the methodsdescribed in the Examples, and they can be controlled by adjusting thestructure of and production method for layer A.

The separators of the first and second embodiments are interchangeableand may also be combined with each other. The separators of the firstand second embodiments may also optionally include a layer other thanthe microporous membrane and inorganic porous layer. The constituentelements of the separators of the first and second embodiments will nowbe described.

[Microporous Membrane]

The microporous membrane may be formed of a polyolefin or a modifiedpolyolefin.

The microporous membrane includes a silane-modified polyolefin, and mayoptionally include other polyolefins. Due to the silane crosslinkingproperty of the silane-modified polyolefin, the microporous membrane isable to undergo crosslinking reaction during the production process forthe separator.

The polyolefin to be included in the microporous membrane is notparticularly restricted, and examples include ethylene or propylenehomopolymers, and copolymers formed from two or more monomers selectedfrom the group consisting of ethylene, propylene, 1-butene,4-methyl-1-pentene, 1-hexene, 1-octene and norbornane. Among these,high-density polyethylene (homopolymer) or low-density polyethylene ispreferred, and high-density polyethylene (homopolymer) is morepreferred, from the viewpoint of allowing heat setting (also abbreviatedas “HS”) to be carried out at higher temperature while avoidingobstruction of the pores. A single polyolefin may be used alone, or twoor more may be used in combination.

From the viewpoint of redox degradation resistance and obtaining acompact, homogeneous porous body structure, the microporous membrane ispreferably produced using both a silane-modified polyolefin andultrahigh molecular weight polyethylene (UHMWPE) as starting materials.The weight-average molecular weight of ultrahigh molecular weightpolyethylene (UHMWPE) is generally known to be 1,000,000 or higher. Morespecifically, the weight ratio of the silane-modified polyolefin andUHMWPE during production of the microporous membrane or separator(silane-modified polyolefin weight/UHMWPE weight) is 0.05/0.95 to0.40/0.60.

The content of the polyolefin in the microporous membrane is preferably50 wt % to 100 wt %, preferably 70 wt % to 100 wt % or preferably 80 wt% to 100 wt %. The microporous membrane also preferably includes apolyolefin with a weight-average molecular weight of 100,000 or higherand less than 1,000,000 (included in a proportion of preferably 40 wt %or greater and more preferably 80 wt % or greater with respect to theentire polyolefin). The weight-average molecular weight of thepolyolefin is more preferably 120,000 or higher and less than 950,000,and even more preferably 130,000 or higher and less than 930,000. Byusing a polyolefin having a weight-average molecular weight of 100,000or higher and less than 1,000,000, relaxation of shrinkage of thepolymer will take place early during a heating test of the electricitystorage device, and in particular, safety will be more easily maintainedin a heating safety test. By adjusting the weight-average molecularweight of the microporous membrane to lower than 1,000,000 it ispossible to inhibit casting defects (film patterns) during extrusion,known as “melt fracture”. By adjusting the weight-average molecularweight of the microporous membrane to 100,000 or higher, on the otherhand, it is possible to inhibit transfer of recesses when themicroporous membrane has been wound around a core (winding core).

The viscosity-average molecular weight of the microporous membraneduring removal of the inorganic porous layer and during uncrosslinkedtreatment is preferably 100,000 to 1,200,000 and more preferably 150,000to 800,000, from the viewpoint of avoiding generation of polymer powderby abrasive shear when the separator is transported by a roll.

The membrane thickness of the microporous membrane is preferably 1.0 μmor greater, more preferably 2.0 μm or greater and even more preferably3.0 μm or greater, 4.0 μm or greater or 4.5 μm or greater. A microporousmembrane thickness of 1.0 μm or greater will tend to result in increasedmembrane strength. The membrane thickness of the microporous membrane isalso preferably no greater than 500 μm, more preferably no greater than100 μm and more preferably no greater than 80 μm, no greater than 22 μmor no greater than 19 μm. A microporous membrane thickness of no greaterthan 500 μm will tend to result in increased ion permeability. Themembrane thickness of the microporous membrane can be measured by themethod described in the Examples.

[First Porous Layer (Layer A)]

Layer A includes a silane-modified polyolefin and has a crosslinkedstructure. From the viewpoint of ensuring degradation resistance againstoxidation-reduction and ensuring a compact, homogeneous porous bodystructure, layer A preferably further includes polyethylene as adifferent polyolefin from the silane-modified polyolefin. Layer A mayalso include components other than the silane-modified polyolefin andpolyethylene.

The polyolefin composing the silane-modified polyolefin in layer A maybe a homopolymer of ethylene or propylene; or a copolymer formed fromtwo or more monomers selected from the group consisting of ethylene,propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene andnorbornane. Among these, the polyolefin is preferably ethylenehomopolymer (polyethylene), more preferably high-density polyethyleneand/or low-density polyethylene and even more preferably high-densitypolyethylene, from the viewpoint of allowing heat setting at highertemperature while avoiding obstruction of the pores. A single polyolefinmay be used alone, or two or more may be used in combination.

Layer A may also include a polymer (another polymer) other than asilane-modified polyolefin or polyethylene, within a range that does notoverly inhibit the effect of the invention.

The weight-average molecular weight of layer A as a whole is preferably100,000 to 1,200,000 and more preferably 150,000 to 800,000.

(Thickness of Layer A)

The thickness (TA) of layer A is preferably 1 μm or greater, morepreferably 2 μm or greater and even more preferably 3 μm or greater. Ifthe thickness (TA) is 1 μm or greater the membrane strength will tend tobe further increased. The thickness (TA) of layer A is also preferably500 μm or smaller, more preferably 100 μm or smaller and even morepreferably 80 μm or smaller. If the thickness (TA) is 500 μm or smallerthe ion permeability will tend to be further increased. The thickness(TA) may be set to 1.00 μm or greater, 2.00 μm or greater or 3.00 μm orgreater, for example.

When the separator is a separator for a LIB, the thickness (TA) ispreferably less than 22 μm, more preferably no greater than 21 μm andeven more preferably no greater than 20.5 μm. When the separator is aseparator for a LIB the upper limit for the thickness (TA) may be set toless than 13 μm or no greater than 8.5 μm. If the thickness (TA) is 25μm or smaller the ion permeability will tend to be further increased.The thickness (TA) may be set to less than 22.00 μm, 21.00 μm orsmaller, 20.00 μm or smaller, less than 13.00 μm or 8.50 or smaller. Thelower limit for the thickness (TA) may be the same as described above.

The thickness (TA) can be measured by the method described in theExamples, and it can be controlled by varying the stretch ratio of layerA.

When layer A is a single layer, the thickness of layer A is treated asthe thickness (TA). When layer A consists of multiple layers, the totalof the thicknesses of the multiple layers in layer A is treated as thethickness (TA).

The membrane rupture temperature of layer A is preferably 180° C. to220° C., as measured by thermomechanical analysis (TMA). Even when theelectricity storage device has generated abnormal heat release due torunaway reaction, the shutdown function of the separator is expected tostop movement of Li ions, and discharge in the electricity storagedevice or outside of the electricity storage device that results fromit. It is expected that the electricity storage device as a whole isthen cooled by a coolant, thus ensuring the safety. On the other hand,if the membrane rupture temperature of layer A is within the rangespecified above, then the separator will undergo molten rupture and seeponto both electrodes so that the active materials can be coated, thuseven more easily inhibiting heat release even when the electricitystorage device as a whole is not sufficiently cooled, or even if anultra-high temperature range is reached.

The membrane rupture temperature of layer A can be measured by themethod described in the Examples, and it can be controlled by changingthe stretching temperature and/or stretch ratio of layer A.

[Porosity of Microporous Membrane or Layer A]

The porosity of the microporous membrane or layer A is preferably 20% orgreater, more preferably 25% or greater, and even more preferably 28% orgreater, 30% or greater, 32% or greater or 35% or greater. If theporosity is 20% or greater, its ability to follow rapid movement of Liions will be further increased. The porosity is also preferably nogreater than 90%, more preferably no greater than 80% and even morepreferably no greater than 60%. If the porosity is no greater than 90%,the membrane strength will be further increased and self-discharge willtend to be inhibited. The porosity can be measured by the methoddescribed in the Examples, and it can be controlled by changing thestretching temperature and/or stretch ratio during the productionprocess.

[Air Permeability of Microporous Membrane or Layer A]

The air permeability of the microporous membrane or layer A ispreferably 1 second/100 cm³ or greater, more preferably 50 seconds/100cm³ or greater, even more preferably 55 seconds/100 cm³ or greater, andyet more preferably 70 seconds or greater, 90 seconds or greater or 110seconds or greater. If the air permeability is 1 second/100 cm³ orgreater, the balance between the membrane thickness, porosity and meanpore size will tend to be improved. The air permeability is alsopreferably no greater than 400 seconds/100 cm³, more preferably nogreater than 300 seconds/100 cm³ and even more preferably no greaterthan 270 seconds/100 cm³. If the air permeability is no greater than 400seconds/100 cm³, the ion permeability will tend to be further increased.The air permeability can be measured by the method described in theExamples, and it can be controlled by changing the stretchingtemperature and/or stretch ratio during the production process.

[Puncture Strength of Microporous Membrane or Layer A]

The puncture strength of the microporous membrane or layer A ispreferably 200 gf/20 μm or greater and more preferably 300 gf/20 μm orgreater. If the puncture strength is 200 gf/20 μm or greater, then evenif the active materials have dropped out when the laminated stack of theseparator and electrodes has been wound, it will be easier to inhibitmembrane rupture due to the dropped out active materials. It will alsobe possible to reduce the possibility of short circuiting caused byexpansion and contraction of the electrodes during charge-discharge. Thepuncture strength of the microporous membrane or layer A is alsopreferably no greater than 4000 gf/20 μm and more preferably no greaterthan 3800 gf/20 μm. If the puncture strength is no greater than 3500gf/20 μm, then it will be easier to reduce heat shrinkage duringheating. The puncture strength can be measured by the method describedin the Examples, and it can be controlled by changing the stretchingtemperature and/or stretch ratio during the production process.

[Tensile Strength of Microporous Membrane or Layer A]

The tensile strength of the microporous membrane or layer A ispreferably 1000 kgf/cm² or greater, more preferably 1050 kgf/cm² orgreater and even more preferably 1100 kgf/cm² or greater in both the MD(the lengthwise direction, machine direction or flow direction of themembrane or layer A) and the TD (the direction perpendicular to the MD,i.e. the transverse direction of the membrane or layer A). If thetensile strength is 1000 kgf/cm² or greater, then slitting or ruptureduring winding of the electricity storage device will tend to be furtherinhibited, or short circuiting due to contaminants in the electricitystorage device will tend to be further inhibited. The tensile strengthof the microporous membrane or layer A is also preferably no greaterthan 5000 kgf/cm², more preferably no greater than 4500 kgf/cm² and evenmore preferably no greater than 4000 kgf/cm². If the tensile strength isno greater than 5000 kgf/cm², then the microporous membrane or layer Awill undergo earlier relaxation to exhibit weaker contractive forceduring heat testing, thus tending to result in higher safety.

[Tensile Modulus of Microporous Membrane or Layer A]

The tensile modulus of the microporous membrane or layer A is preferablyno greater than 120 N/cm, more preferably no greater than 100 N/cm andeven more preferably no greater than 90 N/cm, in both the MD and TD. Atensile modulus of no greater than 120 N/cm means that the separator fora lithium ion secondary battery is not excessively oriented, and forexample, when the plugging agent such as polyethylene melts and shrinksin a heating test, it will tend to allow the polyethylene to undergoearly stress relaxation, thereby preventing shrinkage of the separatorin the battery and being more likely to prevent short circuiting betweenthe electrodes (that is, it can improve the safety of the separatorduring heating). A low tensile modulus in this range is easily achievedby including polyethylene with a weight-average molecular weight of500,000 or lower in the polyolefin forming the microporous membrane orlayer A. The lower limit for the tensile modulus, on the other hand, ispreferably 10 N/cm or greater, more preferably 30 N/cm or greater andeven more preferably 50 N/cm or greater. The tensile modulus can beappropriately adjusted by adjusting the degree of stretching in theproduction process or by relaxation as necessary after stretching.

<Silane-Modified Polyolefin>

The silane-modified polyolefin has a structure with a polyolefin as themain chain and alkoxysilyl groups grafted onto the main chain. Thesilane-modified polyolefin can be obtained by grafting alkoxysilylgroups onto the main chain of a non-silane-modified polyolefin.

It is presumed that the alkoxysilyl groups are converted to silanolgroups by water hydrolysis, and undergo crosslinking reaction to formsiloxane bonds (with any proportion among structure T1, structure T2 andstructure T3 in the following formula). Alkoxides substituting on thealkoxysilyl groups may be methoxide, ethoxide or butoxide. In thefollowing formula, R may be methyl, ethyl, n-propyl, isopropyl, n-butyl,sec-butyl, isobutyl or tert-butyl.

The main chain and grafts are linked by covalent bonding. The structureof the covalent bonding may be an alkyl, ether, glycol or esterstructure. At the stage before the crosslinking reaction, thesilane-modified polyolefin has a modification degree of no greater than2% of silanol units with respect to the main chain ethylene units.

A preferred silane graft-modified polyolefin is one with a density of0.90 to 0.96 g/cm³ and a melt mass-flow rate (MFR) of 0.2 to 5 g/min at190° C.

From the viewpoint of satisfactorily exhibiting the effect of theinvention, the amount of silane-modified polyolefin is preferably 0.5weight % or greater or 3 weight % or greater, more preferably 4 weight %or greater, and even more preferably 5 weight % or greater or 6 weight %or greater, based on the total weight of the microporous membrane orlayer A. From the viewpoint of cycle properties and safety of theelectricity storage device, the amount of silane-modified polyolefin ispreferably no greater than 40 weight % and more preferably no greaterthan 38 weight %, based on the total weight of the microporous membrane.The amount of silane-modified polyolefin may also be 30 weight % orgreater or 50 weight % or greater, or even 100 weight %, based on thetotal weight of layer A.

The crosslinked structure of the microporous membrane or layer A ispreferably formed by an acid, a base or by swelling.

That is, the crosslinked structure in the microporous membrane or layerA is preferably a crosslinked structure obtained by immersing thetreated product containing the silane-modified polyolefin in a base(base solution) or acid (acid solution) and carrying out silanedehydration condensation reaction to form oligosiloxane bonds. Thecrosslinked structure in this case is a crosslinked structure obtainedby actively promoting crosslinking reaction during the productionprocess for the microporous membrane, layer A or the separator.

(Polyethylene)

Throughout the present specification, the polyethylene that can befurther included in addition to the silane-modified polyolefin (thepolyethylene further included in the microporous membrane or layer A asa polyolefin different from the silane-modified polyolefin) ispolyethylene that is ethylene homopolymer or an alkane unit-containingcopolymer with a weight-average molecular weight of 100,000 to10,000,000.

When the microporous membrane or layer A further includes polyethyleneas a polyolefin different from the silane-modified polyolefin, itscontent is preferably 20 weight % or greater, more preferably 40 weight% or greater and even more preferably 50 weight % or greater, based onthe total amount of the silane-modified polyolefin and polyethylene. Ifthe polyethylene content is 20 weight % or greater it will tend to beeasier to ensure degradation resistance against oxidation-reduction, anda compact, homogeneous porous body structure can be ensured.

The polyethylene content is also preferably no greater than 97 weight %,more preferably no greater than 96 weight % and even more preferably nogreater than 95 weight %. If the polyethylene content is no greater than97 weight % it will be possible to ensure the content of thesilane-modified polyolefin in the microporous membrane or layer A.

(Detection Method for Silane-Modified Polyolefin in Separator)

When the silane-modified polyolefin in the separator is in a crosslinkedstate it is insoluble or has insufficient solubility in organicsolvents, and it is therefore difficult to directly measure thesilane-modified polyolefin content from the separator. In such cases, aspretreatment for the sample, methyl orthoformate which does not undergosecondary reactions may be used to decompose the siloxane bonds tomethoxysilanol, and then solution NMR measurement may be carried out todetect the silane-modified polyolefin in the separator. The pretreatmentexperiment may be conducted with reference to Japanese PatentPublication No. 3529854 and Japanese Patent Publication No. 3529858.

Specifically, ¹H or ¹³C NMR identification of the silane-modifiedpolyolefin as the starting material used for production of the separatormay be employed in the detection method for the silane-modifiedpolyolefin in the separator. The following are examples of ¹H— and¹³C—NMR measurement methods.

(¹H-Nmr Measurement)

The sample is dissolved in o-dichlorobenzene-d4 at 140° C. and a ¹H-NMRspectrum is obtained at a proton resonance frequency of 600 MHz. The¹H-NMR measuring conditions are as follows.

Apparatus: AVANCE NEO 600 by Bruker

Sample tube diameter: 5 mmφ

Solvent: o-Dichlorobenzene-d4

Measuring temperature: 130° C.

Pulse angle: 30°

Pulse delay time: 1 sec

Number of scans: 1000

Sample concentration: 1 wt/vol %

(¹³C-Nmr Measurement)

The sample is dissolved in o-dichlorobenzene-d4 at 140° C. and a ¹³C-NMRspectrum is obtained. The ¹³C-NMR measuring conditions are as follows.

Apparatus: AVANCE NEO 600 by Bruker

Sample tube diameter: 5 mmφ

Solvent: o-Dichlorobenzene-d4

Measuring temperature: 130° C.

Pulse angle: 30°

Pulse delay time: 5 sec

Number of scans: 10,000

Sample concentration: 10 wt/vol %

FIGS. 4 and 5 are ¹H and ¹³C-NMR charts for silane-modified polyolefinstarting materials 1 and 2 using two types of polyolefins, wherestarting materials 1 and 2 each have a different melt index (MI), C₃graft amount, C₄ graft amount and/or silanol-modified amount.

The ¹H and ¹³C-NMR measuring conditions for FIG. 4 are as follows.

(¹H-NMR Measuring Conditions)

Apparatus: Bruker Avance NEO 600

Observation nucleus: ¹H

Observation frequency: 600 MHz

Pulse program: zg30

Pulse delay time: 1 sec

Number of scans: 1024

Measuring temperature: 130° C.

Chemical shift reference: 7.219 ppm (o-DCBz)

Solvent: o-Dichlorobenzene-d4

Sample concentration: 1 wt/vol %

Sample tube: 5 mmφ

(¹³C-NMR Measuring Conditions)

Apparatus: Bruker Avance NEO 600

Observation nucleus: ¹³C

Observation frequency: 150.91 MHz

Pulse program: zgpg30

Pulse delay time: 5 sec

Number of scans: 24,000 or 12,800

Measuring temperature: 130° C.

Chemical shift reference: 132.39 ppm (o-DCBz)

Solvent: o-Dichlorobenzene-d4

Sample concentration: 10 wt/vol %

Sample tube: 5 MMφ

The ¹H and ¹³C-NMR measuring conditions for FIG. 5 are as follows.

(¹H-NMR Measuring Conditions)

Apparatus: Bruker Avance NEO 600

Observation nucleus: ¹H

Observation frequency: 600 MHz

Pulse program: zg30

Pulse delay time: 1 sec

Number of scans: 1024

Measuring temperature: 130° C.

Chemical shift reference: 7.219 ppm (o-DCBz)

Solvent: o-Dichlorobenzene-d4

Sample concentration: 1 wt/vol %

Sample tube: 5 mmφ

(¹³C-NMR Measuring Conditions)

Apparatus: Bruker Avance NEO 600

Observation nucleus: ¹³C

Observation frequency: 150.91 MHz

Pulse program: zgpg30

Pulse delay time: 5 sec

Number of scans: 12800

Measuring temperature: 130° C.

Chemical shift reference: 132.39 ppm (o-DCBz)

Solvent: o-Dichlorobenzene-d4

Sample concentration: 10 wt/vol %

Sample tube: 5 mmφ

FIG. 6 shows an ¹H— and ¹³C—NMR chart of the separator fabricated usingsilane-modified polyolefin starting material 1, shown in FIG. 4 , in thestate before crosslinking. The ¹H and ¹³C-NMR measuring conditions forFIG. 6 are as follows.

(¹H-NMR Measuring Conditions)

Apparatus: Bruker Avance NEO 600

Observation nucleus: ¹H

Observation frequency: 600 MHz

Pulse program: zg30

Pulse delay time: 1 sec

Number of scans: 1024

Measuring temperature: 130° C.

Chemical shift reference: 7.219 ppm (o-DCBz)

Solvent: o-Dichlorobenzene-d4

Sample concentration: 1 wt/vol %

Sample tube: 5 MMφ

(¹³C-NMR Measuring Conditions)

Apparatus: Bruker Avance NEO 600

Observation nucleus: ¹³C

Observation frequency: 150.91 MHz

Pulse program: zgpg30

Pulse delay time: 5 sec

Number of scans: 24,000 or 12,800

Measuring temperature: 130° C.

Chemical shift reference: 132.39 ppm (o-DCBz)

Solvent: o-Dichlorobenzene-d4

Sample concentration: 10 wt/vol %

Sample tube: 5 MMφ

For the separator in the crosslinked state, measurement can be performedby NMR in the same manner as FIG. 6 after the pretreatment describedabove (not shown).

As shown in FIGS. 4 to 6 , ¹H and/or ¹³C NMR measurement allows theamount of silane unit modification and the amount of polyolefin alkylgroup modification in the silane-modified polyolefin to be confirmed fora polyolefin starting material, and allows the silane-modifiedpolyolefin contained in the separator to be determined (—CH₂—Si: ¹H,0.69 ppm, t; ¹³C, 6.11 ppm, s).

[Combination of Microporous Membrane and Inorganic Porous Layer]

A combination of a silane-modified polyolefin-containing microporousmembrane and an inorganic porous layer will tend to provide both ashutdown function at lower temperatures than 150° C. and membranerupture properties at relatively high temperature, and to improve theelectricity storage device cycle characteristics and battery nailpenetration safety. Since the silane-modified polyolefin in themicroporous membrane has a silane crosslinking property, presumablysilane crosslinking can result in increased viscosity of the resin inthe microporous membrane, and therefore when compressive force isapplied between the electrodes during a period of abnormal hightemperature of the separator-containing electricity storage device, thecrosslinked high-viscosity resin is less likely to flow into theinorganic layer (that is, integration is less likely), and the clearancebetween the electrodes can be adequately ensured and shorting of thebattery can be inhibited.

[Inorganic Porous Layer]

The inorganic porous layer is a layer comprising inorganic particles anda resin binder, and optionally it may further comprise a dispersingagent that disperses the inorganic particles in the binder resin.

The thickness of the inorganic porous layer is preferably 0.5 μm to 10μm, 0.5 μm to 7 μm, 0.5 μm to 5 μm or 0.5 μm to 4 μm, from the viewpointof the ion permeability of the separator, and the charge-dischargecapacity or cycle stability of the electricity storage device. Thethickness of the inorganic porous layer can be determined by the methoddescribed in the Examples.

[Second Porous Layer (Layer B)]

Layer B comprises inorganic particles. Layer B may also comprise a resinbinder. When layer B comprises inorganic particles and a resin binder,layer B may be an inorganic porous layer as described above. Layer B mayalso comprise components other than inorganic particles and a resinbinder.

(Thickness of Layer B)

The thickness (TB) of layer B is preferably 0.2 μm or greater and morepreferably 0.5 μm or greater. If the thickness (TB) is 0.5 μm or greaterthe mechanical strength will tend to be further increased. The thickness(TB) is also preferably smaller than 22 μm, more preferably 20 μm orsmaller and even more preferably 15 μm or smaller. If the thickness (TB)is 30 μm or smaller, the volume of the electricity storage deviceoccupied by the separator will be reduced, which will tend to beadvantageous from the viewpoint of increasing the capacity of theelectricity storage device. It is also preferred from the viewpoint ofpreventing excessive increase in the air permeability of the separator.The thickness (TB) may be set to 0.50 μm or greater, 0.80 μm or greateror 1.00 μm or greater, or set to smaller than 22.00 μm, 20.00 μm orsmaller or 15.00 μm or smaller, for example.

The thickness (TB) can be measured by the method described in theExamples, and it can be controlled by varying the coating amount of thecoating solution (slurry) used to form layer B.

When layer B is a single layer, the thickness of layer B is treated asthe “thickness (TB)”. When layer B is multi-layered, the total thicknessof the multiple layers of layer B is treated as the “thickness (TB)”.

When layer B is disposed on both one and the other side of layer A, thetotal thickness of the layer B disposed on the one side and the layer Bdisposed on the other side is treated as the “thickness (TB)”.

(Inorganic Particles)

Examples for the inorganic particles include inorganic oxides(oxide-based ceramics) such as alumina (Al₂O₃), silica, titania,zirconia, magnesia, ceria, yttria, zinc oxide and iron oxide; inorganicnitrides (nitride-based ceramics) such as silicon nitride, titaniumnitride and boron nitride; ceramics such as silicon carbide, calciumcarbonate, magnesium sulfate, aluminum sulfate, aluminum hydroxide,aluminum hydroxide oxide (AlO(OH)), potassium titanate, talc, kaolinite,dickite, nacrite, halloysite, pyrophyllite, montmorillonite, sericite,mica, amesite, bentonite, asbestos, zeolite, calcium silicate, magnesiumsilicate, diatomaceous earth and quartz sand; and glass fibers. Thesemay be used alone, or two or more may be used in combination.

From the viewpoint of ensuring heat resistance, the amount of inorganicparticles is preferably 5 weight % or greater or 20 weight % or greater,and more preferably 30 weight % or greater, based on the total weight ofthe inorganic porous layer or layer B. The amount of inorganic particlesmay be set to 50 weight % or greater, greater than 80 weight % or 85weight % or greater, based on the total weight of the inorganic porouslayer or layer B. The amount of inorganic particles is also preferablyno greater than 99.9 weight %, and more preferably no greater than 99.5weight % or no greater than 99 weight %.

The amount of inorganic particles may be set 20.00 weight % or greater,30.00 weight % or greater, 50.00 weight % or greater, greater than 80.00weight % or 85.00 weight % or greater, and also set to no greater than99.90 weight % or 99.50 weight %.

The form of the inorganic particles may be tabular, scaly, needle-like,columnar, spherical, polyhedral, fusiform or aggregated (block-shaped).Inorganic particles with these shapes may also be combined for use.

The number-mean particle size of the inorganic particles is preferably0.01 μm or greater, 0.1 μm or greater, 0.3 μm or greater or 0.5 μm orgreater. The number-mean particle size is also preferably no greaterthan 10.0 μm, no greater than 9.0 μm, no greater than 6.0 μm or nogreater than 2.5 μm, more preferably no greater than 2.0 μm and evenmore preferably no greater than 1.5 μm, for example. Adjusting thenumber-mean particle size of the inorganic particles to within thisrange is preferred from the viewpoint of increasing the safety duringshort circuiting. The method of adjusting the number-mean particle sizeof the inorganic particles may be a method of pulverizing the inorganicparticles using a suitable pulverizing apparatus such as a ball mill,bead mill or jet mill.

The particle size distribution of the inorganic particles is preferably0.02 μm or greater, more preferably 0.05 μm or greater and even morepreferably 0.1 μm or greater, as the minimum particle size. The maximumparticle size is preferably no greater than 20 μm, more preferably nogreater than 10 μm and even more preferably no greater than 7 μm. Themaximum particle size/mean particle size ratio is preferably no greaterthan 50, more preferably no greater than 30 and even more preferably nogreater than 20. Adjusting the particle size distribution of theinorganic particles to within this range is preferred from the viewpointof inhibiting heat shrinkage at high temperature. Multiple particle sizepeaks may also be present between the maximum particle size and minimumparticle size. The method of adjusting the particle size distribution ofthe inorganic particles may be, for example, a method of pulverizing theinorganic filler using a ball mill, bead mill or jet mill to adjust themto the desired particle size distribution, or a method of preparingmultiple fillers with different particle size distributions and thenblending them.

(Resin Binder)

The resin binder comprises a resin that binds together the inorganicparticles. The glass transition temperature (Tg) of the resin binder ispreferably −50° C. to 100° C. and more preferably −35° C. to 95° C.,from the viewpoint of ensuring the binding property with the inorganicparticles, and ensuring stability of the inorganic porous layer or layerB, during the production process for the separator, the productionprocess for the electricity storage device or the charge-dischargeprocess.

The glass transition temperature is determined from a DSC curve obtainedby differential scanning calorimetry (DSC). Specifically, the value usedfor the glass transition temperature may be the temperature at theintersection between a straight line extending the low-temperature endbaseline in the DSC curve toward the high-temperature end, and thetangent line at the inflection point in the stepwise change region ofglass transition. More specifically, it may be determined by the methoddescribed in the Examples. Moreover, the “glass transition” refers tothe value when a change in heat quantity accompanying the change instate of a polymer test piece in DSC occurs at the endothermic end. Thechange in heat quantity is observed in the form of a stepwise change inthe DSC curve. A “stepwise change” is a portion of the DSC curve movingaway from the previous low-temperature end baseline and toward a newhigh-temperature end baseline. A combination of a stepwise change and apeak is also included in the concept of “stepwise change”. The“inflection point” is the point at which the slope of the DSC curve ismaximum in the stepwise change region. If the exothermic end in thestepwise change region is defined as the top end, then this representsthe point where the upwardly convex curve changes to a downwardly convexcurve. The term “peak” refers to a portion of the DSC curve that movesaway from the low-temperature end baseline and then returns to the samebaseline. The term “baseline” refers to the DSC curve in the temperaturezone where no transition or reaction takes place in the test piece.

Examples for the resin binder include the following 1) to 7), forexample. These may be used alone, or two or more may be used incombination.

1) Polyolefins: Polyethylene, polypropylene, ethylene-propylene rubberand modified forms of these;

2) Conjugated diene-based polymers: For example, styrene-butadienecopolymers and their hydrogenated forms, acrylonitrile-butadienecopolymers and their hydrogenated forms andacrylonitrile-butadiene-styrene copolymers and their hydrogenated forms;

3) Acrylic-based polymers: For example, methacrylic acid ester-acrylicacid ester copolymers, styrene-acrylic acid ester copolymers andacrylonitrile-acrylic acid ester copolymers;

4) Polyvinyl alcohol-based resins: For example, polyvinyl alcohol andpolyvinyl acetate;

5) Fluorine-containing resins: For example, PVdF,polytetrafluoroethylene, vinylidenefluoride-hexafluoropropylene-tetrafluoroethylene copolymer andethylene-tetrafluoroethylene copolymer;

6) Cellulose derivatives: For example, ethyl cellulose, methylcellulose, hydroxyethyl cellulose and carboxymethyl cellulose; and

7) Polymers that are resins with a melting point and/or glass transitiontemperature of 180° C. or higher, or without a melting point but havinga decomposition temperature of 200° C. or higher: For example,polyphenylene ethers, polysulfones, polyethersulfones, polyphenylenesulfides, polyetherimides, polyamideimides, polyamides and polyesters.

These types of resin binders can be obtained by known production methodssuch as emulsion polymerization or solution polymerization, using anydesired monomers as the starting materials. The polymerization is notrestricted in terms of the polymerization temperature, the pressureduring polymerization, the method of adding the monomers and theadditives used (polymerization initiator, molecular weight modifier andpH regulator, etc.).

The amount of resin binder is 0.5 weight % or greater or 1.0 weight % orgreater, for example, and no greater than 50 weight % or no greater than30 weight %, for example, based on the total weight of the inorganicporous layer or layer B. Since layer B has the resin binder as anoptional component as mentioned above, the amount of resin binder inlayer B may be less than 20 weight %, 15 weight % or less or 0 weight %based on the total weight of layer B. If the amount of resin binder inlayer B is reduced, it will be possible to increase the amount ofinorganic particles added to layer B by that amount.

(Dispersing Agent)

The dispersing agent is adsorbed onto the surfaces of the inorganicparticles in the slurry to form the inorganic porous layer or layer B,thus stabilizing the inorganic particles by electrostatic repulsion andthe like, and examples thereof include polycarboxylic acid salts,sulfonic acid salts, polyoxyethers and surfactants. The inorganic porouslayer or layer B may also include other components commonly added toaqueous coating materials in addition to the components mentioned above,within the range of the aforementioned effect. Such other componentsinclude, but are not limited to, thickeners, membrane-forming aids,plasticizers, crosslinking agents, cryoprotectants, antifoaming agents,dyes, antiseptic agents, ultraviolet absorbers and light stabilizers,for example. Such other components may be used alone, or two or more maybe used in combination.

(Additives)

The microporous membrane, inorganic porous layer, layer A and/or layer Bmay also include known additives as necessary. Examples of suchadditives include organometallic catalysts (dehydrating condensationcatalysts); plasticizers; phenol-based, phosphorus-based andsulfur-based antioxidants; metal soaps such as calcium stearate and zincstearate; thickeners; membrane-forming aids; crosslinking agents;cryoprotectants; antifoaming agents; antiseptic agents; ultravioletabsorbers; light stabilizers; antistatic agents; anti-fogging agents;dyes; and color pigments.

Layer B may also include a crosslinking agent. The crosslinking agentmay include a functional group that reacts with the inorganic particles.

<Physical Properties of Separator>

When the separator is to be used in a relatively high-capacity lithiumion secondary battery, the membrane thickness of the separator as awhole is preferably no greater than 25 μm, more preferably no greaterthan 22 μm or no greater than 20 μm, even more preferably no greaterthan 18 μm and most preferably no greater than 16 μm. If the membranethickness of the separator is no greater than 25 μm, the ionpermeability will tend to be further increased. The lower limit for themembrane thickness of the separator as a whole may be 1.0 μm or greater,3.0 μm or greater, 4.0 μm or greater, 6.0 μm or greater or 7.5 μm orgreater, for example.

The air permeability of the separator is preferably 50 seconds/100 cm³to 400 seconds/100 cm³, more preferably 75 seconds/100 cm³ to 275seconds/100 cm³ and even more preferably 100 seconds/100 cm³ to 200seconds/100 cm³. This is preferred because the separator will havesuitable mechanical strength so long as the air permeability is 50seconds/100 cm³ or greater, and will have an improved batterycharacteristic from the viewpoint of permeability if the airpermeability is 400 seconds/100 cm³ or less.

<Electricity Storage Device>

The separator described above can be used in an electricity storagedevice. The electricity storage device comprises a separator accordingto the first embodiment, disposed between a plurality of electrodes, andan electrolyte solution. The electrodes are a positive electrode and anegative electrode, for example, with the separator preferably beingdisposed between the positive and negative electrodes. Specifically, theelectricity storage device may be a lithium battery, lithium secondarybattery, lithium ion secondary battery, sodium secondary battery, sodiumion secondary battery, magnesium secondary battery, magnesium ionsecondary battery, calcium secondary battery, calcium ion secondarybattery, aluminum secondary battery, aluminum ion secondary battery,nickel hydrogen battery, nickel cadmium battery, electrical double layercapacitor, lithium ion capacitor, redox flow battery, lithium sulfurbattery, lithium-air battery or zinc air battery, for example. Preferredamong these, from the viewpoint of practicality, are a lithium battery,lithium secondary battery, lithium ion secondary battery, nickelhydrogen battery or lithium ion capacitor, with a lithium battery orlithium ion secondary battery being more preferred.

<Lithium Ion Secondary Battery>

A lithium ion secondary battery is a battery employing a lithiumtransition metal oxide such as lithium cobaltate or a lithium cobaltcomposite oxide as the positive electrode, a carbon material such asgraphite as the negative electrode, and an organic solvent containing alithium salt such as LiPF₆ as the electrolyte solution. The electrolytesolution described above for the method of producing the separator mayalso be used in the lithium ion secondary battery. During charge anddischarge of the lithium ion secondary battery, ionized lithiumreciprocates between the electrodes. The separator is disposed betweenthe electrodes since the ionized lithium must migrate between theelectrodes relatively rapidly while contact between the electrodes isinhibited.

<Method for Producing Separator for Electricity Storage Device>

Another aspect of the invention is a method for producing a separatorfor an electricity storage device. The method for producing theseparator may comprise a step of producing the microporous membrane orlayer A, and optionally a step of producing an inorganic porous layer onthe microporous membrane or a step of producing layer B on layer A. Thematerials used in the method for producing the separator may be thosementioned for the first or second embodiment, unless otherwisespecified.

Third Embodiment

The method for producing a microporous membrane according to a thirdembodiment comprises the following steps:

(1) a sheet-forming step;

(2) a stretching step;

(3) a porous body-forming step;

(4) a heat treatment step;

(5) an affinity treatment step;

(6) a crosslinking step; and

(7) a washing and drying step. Layer A described above can be formed bycarrying out steps (1) to (7). If desired, the method for producing themicroporous membrane according to the third embodiment may also includea kneading step before the sheet-forming step (1) and/or a winding stepafter the washing and drying step (7).

The method for producing a separator may also optionally include thefollowing step in addition to steps (1) to (7):

(8A) a step of coating the inorganic porous layer onto thesilane-crosslinked microporous membrane.

Since the inorganic porous layer is coated in step (8A) onto themicroporous membrane that has been silane-crosslinked in steps (1) to(7), this tends to improve the coatability onto the microporous membraneand the wettability of the microporous membrane in the separatorproduction process.

[Kneading Step]

The kneading step is a step in which the silane graft-modifiedpolyolefin and the other polyolefin are kneaded to obtain a kneadedblend. Polyethylene is preferably used together with the silanegraft-modified polyolefin during the kneading step. The silanegraft-modified polyolefin, the silane-unmodified polyethylene and theother polyolefin may be ones explained for the first embodiment.Optionally, the silane graft-modified polyolefin and a plasticizer maybe kneaded during the kneading step.

In addition, in the kneading step it is preferred to use a polyolefincomposition including a polyolefin with a weight-average molecularweight of lower than 1,000,000 (included in a proportion of preferably40 weight % or greater and more preferably 80 weight % or greater withrespect to the total polyolefin). By using a polyolefin having aweight-average molecular weight of lower than 1,000,000, relaxation ofshrinkage of the polymer will take place early during a heating test ofthe electricity storage device, and in particular, safety will be moreeasily maintained in a heating safety test. When a polyolefin with aweight-average molecular weight of lower than 1,000,000 is used, theelastic modulus in the thickness direction of the obtained microporousmembrane tends to be lower compared to when a polyolefin of 1,000,000 orhigher is used, and therefore a microporous membrane is obtained withrelatively easier transfer of core irregularities.

The polyolefin composition used in the kneading step may containpublicly known additives such as a dehydrating condensation catalyst, aplasticizer, a metal soap such as calcium stearate or zinc stearate, anultraviolet absorber, a light stabilizer, an antistatic agent, ananti-fogging agent or a color pigment.

(Dehydrating Condensation Catalyst)

The alkoxysilyl groups form siloxane bonds by hydrolysis with water.Because the reaction rate is slow, however, an organometallic catalystis usually used to accelerate the condensation reaction. The metal ofthe organometallic catalyst may be one or more selected from the groupconsisting of scandium, vanadium, copper, zinc, zirconium, palladium,gallium, tin, titanium, iron, nickel and lead, for example. Theorganometallic catalyst may be di-butyltin-di-laurate,di-butyltin-di-acetate or di-butyltin-di-octoate, in particular, whichare known to overwhelmingly accelerate the reaction rate by the reactionmechanism proposed by Weij et al. (F. W. van. der. Weij: Macromol.Chem., 181, 2541, 1980.), but in recent years, in order to avoid damageto the environment and human health by organic tin, it is known that theLewis functions of chelate complexes of copper or titanium can beenutilized and combined with organic bases to promote reaction formingsiloxane bonds between alkoxysilyl groups, similar to organic tincomplexes.

(Master Batch Resin)

Dehydrating condensation catalysts are also known to function ascatalysts for siloxane bond-forming reactions with alkoxysilylgroup-containing resins. Throughout the present specification, the term“master batch resin” will be used to refer to a compounded productobtained by pre-adding a dehydrating condensation catalyst (ororganometallic catalyst) to an alkoxysilyl group-containing resin orother kneaded resin in a continuous process with a step of kneading aresin using an extruder.

(Plasticizer)

The plasticizer is not particularly restricted, and examples includeorganic compounds that can form homogeneous solutions with polyolefinsat temperatures below their boiling points. More specifically, theseinclude decalin, xylene, dioctyl phthalate, dibutyl phthalate, stearylalcohol, oleyl alcohol, decyl alcohol, nonyl alcohol, diphenyl ether,n-decane, n-dodecane and paraffin oil. Paraffin oil and dioctylphthalate are preferred among these. A plasticizer may be used alone, ortwo or more may be used in combination.

The proportion of the plasticizer with respect to the total weight ofthe polyolefin is preferably 20 weight % or greater from the viewpointof the porosity of the obtained microporous membrane, and preferably nogreater than 90 weight % for the viewpoint of the viscosity during meltkneading.

[Sheet-Forming Step (Extrusion Step)]

The sheet-forming step is a step in which the obtained kneaded blend ora mixture of the silane graft-modified polyolefin, polyethylene andplasticizer is extruded, cooled to solidification, and cast into a sheetform to obtain a sheet. The sheet forming method is not particularlyrestricted, and may be a method of compressed-cooling solidification ofa molten mixture obtained by melt kneading and extrusion. The coolingmethod may be (i) a method of direct contact with a cooling medium suchas cooling water; or (ii) a method of contact with a refrigerant-cooledroll or a pressing machine, with method (ii) being preferred forsuperior membrane thickness control.

From the viewpoint of resin aggregates in the separator, and the maximuminternal heat release rate, the weight ratio of the silanegraft-modified polyolefin and polyethylene in the sheet-forming step(silane graft-modified polyolefin weight/polyethylene weight) ispreferably 0.05/0.95 to 0.40/0.60 and more preferably 0.06/0.94 to0.38/0.62.

[Stretching Step]

The stretching step is a step in which the plasticizer or inorganicmaterial is extracted from the obtained sheet as necessary, and thesheet is further subjected to stretching in one or more axialdirections. The method of stretching the sheet may be MD uniaxialstretching with a roll stretcher, TD uniaxial stretching with a tenter,sequential biaxial stretching with a combination of a roll stretcher andtenter, or a tenter and tenter, or simultaneous biaxial stretching witha biaxial tenter and inflation molding. Simultaneous biaxial stretchingis preferred from the viewpoint of obtaining a more homogeneousmembrane.

The total area increase is preferably 8-fold or greater, more preferably15-fold or greater and even more preferably 20-fold or greater or30-fold or greater, from the viewpoint of membrane thicknesshomogeneity, and balance between tensile elongation, porosity and meanpore size. If the total area increase is 8-fold or greater, it will tendto be easier to obtain high strength and a satisfactory thicknessdistribution. The area increase is also no greater than 250-fold fromthe viewpoint of preventing rupture.

[Porous Body-Forming Step (Extraction Step)]

The porous body-forming step is a step in which the plasticizer isextracted from the stretched sheet after the stretching step to formpores in the stretched sheet.

The method of extracting the plasticizer is not particularly restricted,and may be a method of immersing the stretched sheet in an extractionsolvent or a method of showering the stretched sheet with an extractionsolvent, for example. The extraction solvent used is not particularlyrestricted, but it is preferably one that is a poor solvent for thepolyolefin and a good solvent for the plasticizer and inorganicmaterial, and that has a boiling point that is lower than the meltingpoint of the polyolefin. Such extraction solvents are not particularlyrestricted and include hydrocarbons such as n-hexane and cyclohexane;halogenated hydrocarbons such as methylene chloride,1,1,1-trichloroethane and fluorocarbon-based compounds; alcohols such asethanol and isopropanol; ketones such as acetone and 2-butanone; andalkali water. An extraction solvent may be used alone, or two or moremay be used in combination.

[Heat Treatment Step]

The heat treatment step is a step in which, after the stretching step,the plasticizer is also extracted from the sheet as necessary and heattreatment is further carried out to obtain a microporous membrane.

The method of heat treatment is not particularly restricted, and forexample, it may be a heat setting method in which a tenter or rollstretcher is utilized for stretching and relaxation procedures. Arelaxation procedure is a procedure of shrinking carried out at aprescribed temperature and relaxation factor, in the machine direction(MD) and/or transverse direction (TD) of the membrane. The relaxationfactor is the value of the MD dimension of the membrane after therelaxation procedure divided by the MD dimension of the membrane beforethe procedure, or the value of the TD dimension after the relaxationprocedure divided by the TD dimension of the membrane before theprocedure, or the product of the relaxation factor in the MD and therelaxation factor in the TD, when both the MD and TD have been relaxed.

For this embodiment, stretching and relaxation in the TD of the porousbody is preferred from the viewpoint of obtaining a heat-treated porousbody suitable for the affinity treatment step and crosslinking step.

[Affinity Treatment Step]

The affinity treatment step is a step in which the microporous membraneobtained in the heat treatment step is immersed in an organic solventthat is amphiphilic for water and organic materials, and which iscarried out in order to improve the wettability between the polyolefinand water. Since an amphiphilic organic solvent is disposed inside theaffinity-treated porous body for this embodiment, it increases affinitywith the liquid, and may also increase the affinity between the materialor catalyst that promotes the crosslinking reaction during thecrosslinking step.

The organic solvent used is not particularly restricted, and examplesinclude alcohols, acetone, ethylene carbonate, N-methyl-2-pyrrolidoneand dimethyl sulfoxide. The method of immersion may be a method ofimmersing the heat-treated porous body in an organic solvent or a methodof showering the heat-treated porous body with an organic solvent.

[Crosslinking Step]

The crosslinking step is a step in which the alkoxysilyl groups in themicroporous membrane obtained by the affinity treatment step are reactedto form siloxane bonds (crosslinking reaction).

For this embodiment, the affinity-treated porous body is contacted witha mixture of an organometallic catalyst and water or is immersed in abase solution or acid solution for silane dehydration condensationreaction, to form oligosiloxane bonds.

For common molded articles such as hot water pipes, a Sn-based catalystis loaded into the extruder during the extrusion step, but in aproduction process for a separator for an electricity storage device,accelerated silane crosslinking in the extruder during the sheet-formingstep can lead to poor production of the gelled sections, and difficultstretching of the silane-crosslinked polyolefin during the subsequentstretching step. For this embodiment, therefore, the silane crosslinkingtreatment is carried out after the stretching step, heat treatment stepand affinity treatment step to ensure the heat resistance, shaperetention and rupture resistance of the separator by the silanecrosslinked sections.

The metal of the organometallic catalyst may be one or more selectedfrom the group consisting of scandium, vanadium, copper, zinc,zirconium, palladium, gallium, tin, titanium, iron, nickel and lead, forexample, among which tin, zinc or palladium is preferred, and tin orzinc is more preferred. Examples of organic tin complexes that can beused as catalysts include dibutyltin dilaurate, dibutyltin diacetate,dibutyltin dioctoate, stannous acetate and stannous caprylate.

The base solution may have a pH of higher than 7 and may include alkalimetal hydroxides, alkaline earth metal hydroxides, alkali metalcarbonates, alkali metal phosphates, ammonia or amine compounds, forexample. Of these, alkali metal hydroxides and alkaline earth metalhydroxides are preferred, alkali metal hydroxides are more preferred andsodium hydroxide is even more preferred, from the viewpoint of theelectricity storage device safety and the silane crosslinking property.

The acid solution is a pH of below 7 and may include inorganic acids ororganic acids, for example. Preferred acids are hydrochloric acid,sulfuric acid, carboxylic acids or phosphoric acids.

From the viewpoint of inhibiting thermal runaway reaction duringelectricity storage device destruction, for improved safety, thecrosslinking step is preferably carried out by immersing theaffinity-treated porous body in a base solution or acid solution.

When the affinity-treated porous body is to be immersed in a basesolution, the temperature of the base solution is preferably 20° C. to100° C. and/or the base solution pH is preferably 8 to 14, from theviewpoint of further improving safety. The reagent to be used for pHadjustment is not particularly restricted and may be an alkali metalhydroxide or alkaline earth metal hydroxide. From the same viewpoint,the aqueous alkali solution preferably does not include amine compoundssuch as ethylamine, dibutylamine, hexylamine or pyridine.

Without being constrained by any particular theory, it is believed thatwhen the affinity-treated porous body is immersed in an acid solution,the acid acts to catalytically promote formation of Si—O bonds in thesilane-crosslinked polyolefin rather than breaking the Si—O bonds of thesilane-crosslinked polyolefin.

When the affinity-treated porous body is contacted with a mixture of anorganometallic catalyst and water, from the viewpoint of controlling theamorphous part of the microporous membrane to ensure safety, the contentof scandium, vanadium, copper, zinc, zirconium, palladium, gallium, tin,titanium, iron, nickel or lead in the finally obtained microporousmembrane is preferably adjusted to be in the range of 0.10 ppm to 200ppm as the total in terms of atoms, and more preferably the content ofzinc or tin in the microporous membrane is adjusted to be in the rangeof 0.10 ppm to 200 ppm as the total in terms of atoms. The content ofscandium, vanadium, copper, zinc, zirconium, palladium, gallium, tin,titanium, iron, nickel or lead in the microporous membrane may beadjusted by the washing and drying step described below, for example. Ithas been found that when the metal contents are within this specifiedrange, decomposition of the crosslinked structure of the porous membraneis inhibited and safety is ensured, and the battery cycle characteristicis also satisfactorily exhibited. It has been shown by the presentinventors that when the metals are present in excess in a separator foran electricity storage device, eluting ions infiltrate into the positiveelectrode, altering the structures of the metal clusters that arestoring Li, producing electrical defect points in the positive electrodeas a whole, and impairing the cycle performance.

[Washing and Drying Step]

The washing and drying step is a step in which the microporous membraneobtained in the crosslinking step is washed with water and dried. Thepreferred conditions for the washing and drying step are a watertemperature of 20 to 100° C. and/or a washing water pH of 6 to 8. Forexample, the microporous membrane interior may be replaced with water ata pH of 6 to 8 and a temperature of 20 to 100° C., and then dried. Thedrying method is not particularly restricted and may be transport with aheated roll, blasting of hot air, or heat drying using an infraredheater.

[Inorganic Porous Layer Coating Step]

The coating step (8A) for the inorganic porous layer is a step in whichan inorganic porous layer comprising inorganic particles and a resinbinder is formed on at least one surface of the microporous membraneobtained as described above. The coating step (8A) for the inorganicporous layer may be carried out after the silane crosslinking reactionof the silane graft-modified polyolefin.

Layer B described above can be formed by carrying out the coating step(8A). The method used to form layer B may be a known production method.The method of fabricating a laminated stack comprising layer A and layerB may be, for example, a method of coating an inorganicparticle-containing slurry onto layer A, a method of layering andextruding the starting material for layer B and the starting materialfor layer A by a co-extrusion method, or a method of separatelypreparing layer A and layer B and then attaching them together.

The inorganic porous layer can be formed, for example, by coating atleast one surface of the microporous membrane with a slurry containinginorganic particles, a resin binder, water or an aqueous solvent (forexample, a mixture of water and an alcohol) and optionally a dispersingagent. The inorganic particles, resin binder and dispersing agent may beas described above for the first or second embodiment.

The solvent in the slurry is preferably one that can uniformly andstably disperse or dissolve the inorganic particles. Examples of suchsolvents include N-methylpyrrolidone (NMP), N,N-dimethylformamide,N,N-dimethylacetamide, water, ethanol, toluene, hot xylene, methylenechloride and hexane.

The method of preparing the inorganic particle-containing slurry may be,for example, a mechanical stirring method using a ball mill, bead mill,planetary ball mill, vibrating ball mill, sand mill, colloid mill,attritor, roll mill, high-speed impeller disperser, disperser,homogenizer, high-speed impact mill, ultrasonic disperser or stirringblade.

Examples for the method of coating the inorganic particle-containingslurry include gravure coater methods, small-diameter gravure coatermethods, reverse roll coater methods, transfer roll coater methods, kisscoater methods, dip coater methods, knife coater methods, air doctorcoater methods, blade coater methods, rod coater methods, squeeze coatermethods, cast coater methods, die coater methods, screen printingmethods and spray coating methods.

The method for removing the solvent from the coated membrane may be amethod of drying at a temperature below the melting point of thematerial forming the microporous membrane, or a method of reducedpressure drying at low temperature. Some of the solvent may be allowedto remain so long as it does not produce any notable effect on thedevice properties.

[Winding/Slitting Step]

The winding step is a step in which the obtained microporous membrane orthe inorganic porous layer-coated microporous membrane is slitted ifnecessary and wound onto a prescribed core.

The separator obtained by the method that includes each of the stepsdescribed above may be utilized in an electricity storage device, andparticularly in a lithium battery or lithium ion secondary battery.

<Method for Producing Electricity Storage Device>

The method for producing an electricity storage device comprises thefollowing steps:

(a) a step of laminating and/or winding a positive electrode, aseparator produced by the method of the third embodiment, and a negativeelectrode, to obtain a laminated stack or wound body;

(b) a step of inserting the laminated stack or wound body into anexterior body;

(c) a step of pouring an electrolyte solution into the exterior body;and

(d) a step of connecting lead terminals to the positive electrode andnegative electrode.

Steps (a) to (d) can be carried out by a method known in the technicalfield, except for using a separator for an electricity storage deviceproduced by the method of the third embodiment, and a positiveelectrode, negative electrode, electrolyte solution and exterior bodyknown in the technical field may be used in steps (a) to (d).

A separator with a longitudinal shape having a width of 10 to 500 mm(preferably 80 to 500 mm) and a length of 200 to 4000 m (preferably 1000to 4000 m) may be produced for step (a). Next, in step (a), laminationmay be carried out in the order: positive electrode-separator-negativeelectrode-separator or negative electrode-separator-positiveelectrode-separator, and the laminate wound into a circular or flatspiral form to obtain a wound body. In steps (b) and (c), the wound bodymay be housed in a device can (for example, a battery can) and anonaqueous electrolyte solution injected to produce an electricitystorage device. The electrodes and the wound body obtained by foldingthe separator may then be placed in a device container (for example, analuminum film), which is then filled with a nonaqueous electrolytesolution, thereby producing an electricity storage device.

The wound body may also be pressed during this time. Specifically, theseparator may be stacked and pressed with an electrode having a currentcollector and an active material layer formed on at least one side ofthe current collector.

The pressing temperature is preferably 20° C. or higher, as an exampleof a temperature allowing adhesion to be effectively exhibited. From theviewpoint of inhibiting blocking or heat shrinkage of the pores in theseparator by hot pressing, the pressing temperature is preferably lowerthan the melting point of the material in the microporous membrane, andmore preferably no higher than 120° C. The pressing pressure ispreferably no higher than 20 MPa from the viewpoint of inhibitingblocking of the pores of the separator. The pressing time may be up to 1second when a roll press is used, or several hours for surface pressing,but from the viewpoint of productivity it is preferably no longer than 2hours.

By this production process it is possible to reduce press back duringpress molding of a wound body comprising the electrodes and theseparator. It is thus possible to inhibit yield reduction in the deviceassembly steps and shorten the production process time.

The electrolyte solution to be used in step (c) may include a fluorine(F)-containing lithium salt such as LiPF₆, LiBF₄, LiN(SO₂CF₃)₂ orLiSO₃CF₃, or an electrolyte such as LiBC₄O₈ (LiBOB), but it preferablyincludes a LiPF₆-containing electrolyte or F-containing electrolyte anda nonaqueous solvent.

EXAMPLES

The present invention will now be explained in greater detail byexamples and comparative examples, with the understanding that theinvention is not limited to the examples so long as its gist ismaintained. The physical properties in the examples were measured by thefollowing methods.

<Weight-Average Molecular Weight (Mw)>

Standard polystyrene was measured using a Model ALC/GPC 150C™ by WatersCo. under the following conditions, and a calibration curve was drawn.The chromatogram for each polymer was also measured under the sameconditions, and the weight-average molecular weight of each polymer wascalculated by the following method, based on the calibration curve.

Column: GMH₆-HT™ (2)+GMH₆-HTL™ (2), by Tosoh Corp.

Mobile phase: o-Dichlorobenzene

Detector: differential refractometer

Flow rate: 1.0 ml/min

Column temperature: 140° C.

Sample concentration: 0.1 wt %

(Weight-Average Molecular Weight of Polyethylene)

Each molecular weight component in the obtained calibration curve wasmultiplied by 0.43 (polyethylene Q factor/polystyrene Qfactor=17.7/41.3), to obtain a molecular weight distribution curve interms of polyethylene, and the weight-average molecular weight wascalculated.

(Weight-Average Molecular Weight of Resin Composition)

The weight-average molecular weight was calculated in the same manner asfor polyethylene, except that the Q factor value for the polyolefin withthe largest weight fraction was used.

<Viscosity-Average Molecular Weight (Mv)>

The limiting viscosity [η] (dl/g) at 135° C. in a decalin solvent wasdetermined based on ASTM-D4020. The My of polyethylene was calculated bythe following formula.

[η]=6.77×10⁻⁴ Mv ^(0.67)

<Melt Mass-Flow Rate (MFR) (g/10 Min)>

A melt mass-flow rate measuring device by Toyo Seiki Co., Ltd. (MeltIndexer F-F01) was used to determine the weight of the resin extrudedfor 10 minutes under conditions of 190° C., 2.16 kg pressure, as the MFRvalue.

<Measurement of Glass Transition Temperature>

An appropriate amount of the resin sample-containing aqueous dispersion(solid content=38 to 42 wt %, pH=9.0) was placed in an aluminum pan anddried for 30 minutes with a hot air drier at 130° C. to obtain a drymembrane. Approximately 17 mg of the dried membrane was packed into anmeasuring aluminum container, and DSC and DDSC curves were obtainedusing a DSC measuring apparatus (model DSC6220 by Shimadzu Corp.) undera nitrogen atmosphere. The measuring conditions were as follows.

Stage 1 heating program: Start=70° C., temperature increase at 15°C./min. Temperature maintained for 5 minutes after reaching 110° C.

Stage 2 cooling program: Temperature decrease from 110° C. at 40°C./min. Temperature maintained for 5 minutes after reaching −50° C.

Stage 3 heating program: Temperature decrease from −50° C. to 130° C. at15° C./min. Recording of DSC and DDSC data during stage 3 temperatureincrease.

The intersection between the baseline (an extended straight line towardthe high-temperature end from the baseline of the obtained DSC curve)and the tangent line at the inflection point (the point where theupwardly convex curve changed to a downwardly convex curve) was recordedas the glass transition temperature (Tg).

<Membrane Thickness (μm)>

A KBM™ microthickness meter by Toyo Seiki Co., Ltd. was used to measurethe membrane thickness of the microporous membrane or separator at roomtemperature (23±2° C.) and 60% relative humidity. Specifically, themembrane thickness was measured at 5 points at approximately equalintervals across the entire width in the TD direction, and the averagevalue was calculated. The thickness of the inorganic porous layer can becalculated by subtracting the thickness of the microporous membrane fromthe thickness of the separator comprising the microporous membrane andthe inorganic porous layer.

<Layer a Thickness (TA), Layer B Thickness (TB)>

A KBM™ microthickness meter by Toyo Seiki Co., Ltd. was used to measurethe thickness (TA) of layer A at room temperature (23±2° C.) and 60%relative humidity. Specifically, the membrane thickness was measured at5 points at approximately equal intervals across the entire width in theTD, and the average value was calculated. The thickness of the laminatedstack including layer A and layer B was obtained by the same method. Thethickness (TA) of layer A was subtracted from the thickness of theobtained laminated stack to obtain the thickness (TB) of the layer B.

The thickness of the obtained laminated stack was treated as the totalthickness (TA+TB) of layer A and layer B. The thickness (TA) was dividedby the thickness (TB) to obtain the thickness ratio (TA/TB).

<Porosity (%)>

(i) Calculation from Density of Mixed Composition

A 10 cm×10 cm-square sample was cut out from the microporous membrane,and its volume (cm³) and mass (g) were determined and used together withthe density (g/cm³) by the following formula, to obtain the porosity.The density value used for the mixed composition was the valuedetermined by calculation from the densities of the starting materialsused and their mixing ratio.

Porosity (%)=(Volume−(mass/density of mixed composition))/volume×100

(ii) Calculation from Membrane Density

Alternatively, the porosity of the microporous membrane may becalculated by the following formula from the volume, mass and membranedensity (g/cm³).

Porosity (%)=(Volume−(mass/membrane density))/volume×100

The membrane density, for the purpose of the present disclosure, is thevalue measured according to the density gradient tube method D describedin JIS K7112(1999).

(iii) Porosity of Layer A

A 10 cm×10 cm-square sample was cut out from layer A, and its volume(cm³) and mass (g) were determined and used together with the density(g/cm³) in the following formula, to obtain the porosity. The densityvalue used for the mixed composition was the value determined bycalculation from the densities of the starting materials used and theirmixing ratio.

Porosity (%)=(Volume−(mass/density of mixed composition))/volume×100

<Air Permeability (Sec/100 cm³)>

The air permeability of the sample or layer A was measured with a Gurleyair permeability tester (G-B2™ by Toyo Seiki Kogyo Co., Ltd.), accordingto JIS P-8117(2009).

<Puncture Strength of Layer A>

Using a Handy Compression Tester KES-G5 (model name) by Kato Tech Corp.,layer A was anchored with a specimen holder having an opening diameterof 11.3 mm. Next, the center section of the anchored layer A wassubjected to a puncture test with a needle having a tip curvature radiusof 0.5 mm, at a puncture speed of 2 mm/sec and a 25° C. atmosphere, tomeasure the maximum puncture load. The value of the maximum punctureload per 20 μm thickness was recorded as the puncture strength (gf/20μm). When the thermoplastic polymer is only present on one side of thebase material, the needle may be used for piercing from the side wherethe thermoplastic polymer is present.

<Quantification of Resin Aggregates in Separator>

The resin aggregates in the separator were defined in a region with anarea of 100 μm length x 100 μm width, and with no light permeation, whenseparators obtained by the membrane formation steps in the Examples andComparative Examples described below were observed with a transmissionoptical microscope. The number of resin aggregates per 1000 m² area ofthe separator were counted during observation with a transmissionoptical microscope.

<TMA Membrane Rupture Temperature>

Using a TMA50™ by Shimadzu Corp. in fixed-length mode, the environmentaltemperature is varied from 25 to 250° C. and the temperature at themoment that the load is fully released is established as the TMAmembrane rupture temperature.

Specifically, for measurement in the MD direction, the microporousmembrane was sampled at 3 mm in the TD direction and 14 mm in the MDdirection and both ends of the sample in the MD direction were anchoredwith a chuck to a dedicated probe, an initial load of 1.0 g was appliedwith the chuck distance at 10 mm, and the temperature of a furnace inwhich the test piece had been mounted was increased, recording the TMAmembrane rupture temperature as the temperature at which the load wasshown to be 0 g.

For measurement in the TD direction, the microporous membrane is sampledat 14 mm in the TD direction and 3 mm in the MD direction and both endsin the TD of the sample are anchored with a chuck to a dedicated probe,the chuck distance is set to 10 mm, an initial load of 1.0 g is applied,and the same procedure as above is carried out.

<Membrane Rupture Temperature of Layer A>

Using a TMA50™ by Shimadzu Corp. in fixed-length mode, the environmentaltemperature was varied from 25 to 250° C. and the temperature at themoment that the load was fully released was established as the TMAmembrane rupture temperature (the membrane rupture temperature of layerA, measured by TMA).

Specifically, a sample was taken from layer A at 3 mm in the TD and 14mm in the MD, for use as a sample strip (a sample strip with the longside in the MD). Both ends of the sample strip in the MD were set on adedicated probe with the chuck distance at 10 mm, and a load of 1.0 gwas applied to the sample strip. The furnace in which the test piece hadbeen mounted was increased in temperature, and the membrane rupturetemperature (° C.) was recorded as the temperature at which the load wasshown to be 0 g.

When measuring a sample strip TD with the long side in the TD, layer Ais sampled to 14 mm in the TD and 3 mm in the MD and used as the samplestrip, both ends in the TD of the sample are anchored with a chuck to adedicated probe, the chuck distance is set to 10 mm, an initial load of1.0 g is applied, and the same procedure as above is carried out.

<Heat Shrinkage Factor at 150° C.>

The laminated stack before formation of the crosslinked structure (thelaminated stack comprising layer A and layer B) was sampled at 100 mm inthe TD and 100 mm in the MD, for use as a sample strip. The sample stripwas allowed to stand for 1 hour in an oven at 150° C. During this time,the sample strip was sandwiched between two sheets so that the warm airdid not directly contact with the sample strip. After removing thesample strip from the oven and cooling it, the area of the sample stripwas measured, and the heat shrinkage factor at 150° C. (T1) beforeformation of the crosslinked structure was calculated by the followingformula.

Heat shrinkage factor at 150° C. (%)=(10,000(Mm ²)-area of sample stripafter heating(Mm ²))×100/10,000

The laminated stack after formation of the crosslinked structure wasalso sampled to 100 mm in the TD and 100 mm in the MD to obtain a samplestrip, and the same procedure as above was carried out, to calculate theheat shrinkage factor at 150° C. (T2) after formation of the crosslinkedstructure.

The heat shrinkage factor (T2) was divided by the heat shrinkage factor(T1) to obtain the ratio (T2/T1). The value of the ratio (T2/T1)corresponds to the change in the heat shrinkage factor at 150° C. (T2)after formation of the crosslinked structure with respect to the heatshrinkage factor at 150° C. (T1) before formation of the crosslinkedstructure.

<Battery Destruction Safety Test 1>

Battery destruction safety test 1 is a test in which a battery chargedto 4.5 V is hit with an iron nail at a speed of 20 mm/sec, puncturing itto produce internal short circuiting. This test can measuretime-dependent change behavior of voltage reduction of the battery dueto internal short circuiting, and battery surface temperature increasebehavior due to internal short circuiting, to elucidate these phenomenaduring internal short circuiting. Inadequate shutdown function of theseparator during internal short circuiting or membrane rupture at lowtemperature can also result in sharp heat release of the battery, whichmay lead to ignition of the electrolyte solution and fuming and/orexplosion of the battery.

(Fabrication of Battery to be Used in Battery Destruction Safety Test 1)

1a. Fabrication of Positive Electrode

A slurry was prepared by sampling 92.2 weight % of lithium cobaltcomposite oxide (LiCoO₂) as a positive electrode active material, 2.3weight % each of flaky graphite and acetylene black as conductivematerials and 3.2 weight % of polyvinylidene fluoride (PVDF) as a resinbinder, and dispersing them in N-methylpyrrolidone (NMP). The slurry wascoated using a die coater onto one side of a 20 μm-thick aluminum foilas the positive electrode collector, and dried at 130° C. for 3 minutes,after which it was compression molded using a roll press. During thistime, the active material coating amount on the positive electrode wasadjusted to 250 g/m² and the active material bulk density was adjustedto 3.00 g/cm³.

1b. Fabrication of Negative Electrode

A slurry was prepared by dispersing 96.9 weight % of artificial graphiteas a negative electrode active material, 1.4 weight % of carboxymethylcellulose ammonium salt as a resin binder and 1.7 weight % ofstyrene-butadiene copolymer latex in purified water. The slurry wascoated using a die coater onto one side of a 12 μm-thick copper foil asthe negative electrode collector, and dried at 120° C. for 3 minutes,after which it was compression molded using a roll press. During thistime, the active material coating amount on the negative electrode wasadjusted to 106 g/m² and the active material bulk density was adjustedto 1.35 g/cm³.

1c. Preparation of Nonaqueous Electrolyte Solution

A 1.0 mol/L portion of concentrated LiPF₆, as a solute, was dissolved ina mixed solvent of ethylene carbonate:ethylmethyl carbonate=1:2 (volumeratio), to prepare a nonaqueous electrolyte solution.

1d. Battery Assembly

A separator was cut out to 60 mm in the widthwise (TD) direction and1000 mm in the lengthwise (MD) direction, the separator was folded in ahairpin fashion, and positive electrodes and negative electrodes werealternately stacked between the separator (12 positive electrodes, 13negative electrodes). The positive electrodes used had areas of 30 mm×50mm, and the negative electrodes had areas of 32 mm×52 mm. The laminatedstack that had been folded in a hairpin fashion was inserted into alaminating bag, and then injected with the nonaqueous electrolytesolution obtained in c. above and sealed. After allowing it to stand atroom temperature for 1 day, it was subjected to initial charge of thefabricated battery for a total of 6 hours, by a method of charging to acell voltage of 4.2 V at a current value of 3 mA (0.5 C) in anatmosphere of 25° C. and, after reaching that voltage, beginning to drawout a current of 3 mA while maintaining 4.2 V. The battery was thendischarged to a cell voltage of 3.0 V at a current value of 3 mA (0.5C).

(Maximum Heat Release Rate)

After puncturing the obtained battery with an iron nail, the batterysurface temperature was measured using a thermocouple for a period of300 seconds and the resulting temperature change graph was used todetermine the rate during which the change in temperature increase persecond was greatest, as the maximum heat release rate.

(Voltage Reduction Time)

The time required for voltage reduction from 4.5 V to 3 V afterpuncturing the obtained battery with an iron nail was established as thevoltage reduction time (3 V reduction time).

<Cycle Characteristic Evaluation and Battery Fabrication Method>

A battery for evaluation of cycle characteristics was fabricated by thesame method as in 1a. to 1c. above for the method of fabricating abattery used in <Battery destruction safety test 1>, but with theassembly described in 1d-2. below.

1d-2. Battery Assembly

The separator was cut out to a circle with a diameter of 18 mm and thepositive electrode and negative electrode to circles with diameters of16 mm, and the positive electrode, separator and negative electrode werestacked in that order with the active material sides of the positiveelectrode and negative electrode facing each other, after which theywere housed in a covered stainless steel container. The container andcover were insulated, with the container in contact with the negativeelectrode copper foil and the cover in contact with the positiveelectrode aluminum foil. The nonaqueous electrolyte solution obtained in1c. under <Battery destruction safety test 1> above was injected intothe container, which was then sealed. After allowing it to stand at roomtemperature for 1 day, it was subjected to initial charge of thefabricated battery for a total of 6 hours, by a method of charging to acell voltage of 4.2 V at a current value of 3 mA (0.5 C) in anatmosphere of 25° C. and, after reaching that voltage, beginning to drawout a current of 3 mA while maintaining 4.2 V. The battery was thendischarged to a cell voltage of 3.0 V at a current value of 3 mA (0.5C).

Charge-discharge of the obtained battery was carried out for 100 cyclesin an atmosphere of 60° C. Charging was for a total of 3 hours, by amethod of charging to a cell voltage of 4.2 V at a current value of 6.0mA (1.0 C) and, after reaching that voltage, beginning to draw out acurrent of 6.0 mA while maintaining 4.2 V. Discharge was to a cellvoltage of 3.0 V at a current value of 6.0 mA (1.0 C).

(Cycle Characteristic Evaluation 1)

The capacity retention was calculated from the service capacity at the100th cycle and the service capacity at the first cycle. A high capacityretention was evaluated as a satisfactory cycle characteristic.

(Cycle Characteristic Evaluation 2)

The capacity retention (%) was calculated from the service capacity atthe 300th cycle and the service capacity at the first cycle, based onthe following formula. A high capacity retention was evaluated as asatisfactory cycle characteristic.

Evaluation result (%)=(Retention volume after 100×300cycle/servicecapacity at first cycle)

<Fuse/Meltdown (F/MD) Characteristic> (i) Pressure of 0.5 MPa andTemperature-Elevating Rate of 2° C./Min

A circular positive electrode, separator and negative electrode withdiameters of 200 mm were cut out and stacked, and a nonaqueouselectrolyte solution was added to the obtained laminated stack andallowed to thoroughly permeate it. The laminated stack is insertedbetween the center section of circular aluminum heater with a diameterof 600 mm, and the aluminum heater is pressed vertically with ahydraulic jack to 0.5 MPa, thus completing preparation for themeasurement. The laminated stack is heated with the aluminum heater at atemperature-elevating rate of 2° C./min while measuring the resistance(Q) between the electrodes. Resistance between the electrodes increaseswith fusing of the separator, and the temperature when the resistancefirst exceeds 1000Ω is recorded as the shutdown temperature. Heating iscontinued, and the temperature when the resistance falls below 1000Ω isrecorded as the meltdown temperature (membrane rupture temperature).

(ii) Maximum Pressurization of 10 MPa and Temperature-Elevating Rate of15° C./Min

A circular positive electrode, separator and negative electrode withdiameters of 200 mm were cut out and stacked, and a nonaqueouselectrolyte solution was added to the obtained laminated stack andallowed to thoroughly permeate it. The laminated stack was insertedbetween the center section of circular aluminum heater with a diameterof 600 mm, and the aluminum heater was pressed vertically with ahydraulic jack to a pressure of 10 MPa, thus completing preparation forthe measurement. The laminated stack was heated with the aluminum heaterat a temperature-elevating rate of 15° C./min while measuring theresistance (Q) between the electrodes. Resistance between the electrodesincreased, and the temperature when the resistance first exceeded 1000Ωwas recorded as the shutdown temperature (° C.). Heating was furthercontinued, and the temperature when the resistance fell below 1000Ω wasrecorded as the meltdown temperature (° C.).

For the evaluations of both (i) and (ii), a resistance measurement wirewas bonded with conductive silver paste behind the aluminum foil of thepositive electrode fabricated according to “1a. Fabrication of positiveelectrode” under <Battery destruction safety test 1> above. In addition,a resistance measurement wire was bonded with conductive silver pastebehind the negative electrode copper foil fabricated according to “1b.Fabrication of negative electrode” under <Battery destruction safetytest 1> above. An electrolyte-containing solution prepared according to“1c. Preparation of nonaqueous electrolyte solution” under <Batterydestruction safety test 1> above was also used for the F/MD propertytest.

<Safety Test (Nail Penetration Test) 2>

2a. Fabrication of Positive Electrode

After mixing 90.4 weight % of a nickel, manganese and cobalt compositeoxide (NMC) (Ni:Mn:Co=1:1:1 (element ratio), density: 4.70 g/cm³), asthe positive electrode active material, 1.6 weight % of graphite powder(KS6) (density: 2.26 g/cm³, number-mean particle size: 6.5 μm) and 3.8weight % of acetylene black powder (AB) (density: 1.95 g/cm³,number-mean particle size: 48 nm), as conductive aids, and 4.2 weight %of PVDF (density: 1.75 g/cm³) as a resin binder, the mixture wasdispersed in NMP to prepare a slurry. The slurry was coated using a diecoater onto one side of a 20 μm-thick aluminum foil sheet as thepositive electrode collector, and dried at 130° C. for 3 minutes, afterwhich it was compression molded using a roll press, to fabricate apositive electrode. The coating amount of the positive electrode activematerial was 109 g/m².

2b. Fabrication of Negative Electrode

In purified water there were dispersed 87.6 weight % of graphite powderA (density: 2.23 g/cm³, number-mean particle size: 12.7 μm) and 9.7weight % of graphite powder B (density: 2.27 g/cm³, number-mean particlesize: 6.5 μm) as negative electrode active materials, and 1.4 (solid)weight % of carboxymethyl cellulose ammonium salt (1.83 weight % solidconcentration aqueous solution) and 1.7 (solid) weight % of diene rubberlatex (40 weight % solid concentration aqueous solution) as resinbinders, to prepare a slurry. The slurry was coated using a die coateronto one side of a 12 μm-thick copper foil sheet as the negativeelectrode collector, and dried at 120° C. for 3 minutes, after which itwas compression molded using a roll press to fabricate a negativeelectrode. The coating amount of the negative electrode active materialwas 52 g/m².

2c. Preparation of Nonaqueous Electrolyte Solution

A 1.0 mol/L portion of concentrated LiPF₆, as a solute, was dissolved ina mixed solvent of ethylene carbonate:ethyl methyl carbonate=1:2 (volumeratio), to prepare a nonaqueous electrolyte solution.

2d. Fabrication of Battery

The positive electrode, negative electrode and nonaqueous electrolytesolution obtained in 2a to 2c above, and a separator (a separator of theExamples or a separator of the Comparative Examples) were used tofabricate a laminated secondary battery with a size of 100 mm×60 mm anda capacity of 3 Ah, which was charged with constant current, constantvoltage (CCCV) over a period of 3 hours under conditions with a currentvalue of 1A (0.3 C) and a final cell voltage of 4.2 V.

2e. Nail Penetration Evaluation

The fabricated laminated secondary battery was set on a steel sheet in atemperature-adjustable explosion-proof booth. Setting theexplosion-proof booth interior to a temperature of 40° C., the centersection of the laminated secondary battery was punctured with an ironnail having a diameter of 3.0 mm at a speed of 2 mm/sec, and the nailwas left in the punctured state. A thermocouple had been set inside thenail so as to allow measurement inside the laminated battery afterpuncturing with the nail, and its temperature was measured and thepresence or absence of ignition was evaluated.

The evaluation was repeated using laminated secondary batteries newlyfabricated by the same method, and the number of samples withoutignition (no ignition) was calculated as a percentage value by thefollowing formula.

Evaluation result (%)=(100×number of samples without ignition/totalnumber of samples)

<Extrusion Stability>

The state of the polyolefin composition extruded during the extrusionstep was observed and evaluated on the following scale.

A (Good): Change in current value of extruder within ±0.5A of mean valuefor 300 seconds.

B (Poor): Change in current value of extruder exceeded ±0.5A of meanvalue for 300 seconds.

<Metal Content>

The mass ratios of Sn atoms, Zn atoms, T1 atoms, Cu atoms, Fe atoms andNi atoms in the sample were measured using an inductively coupled plasma(ICP) emission analyzer.

<Experiment Group I> [Silane Graft-Modified Polyolefin ProductionMethod]

The polyolefin starting material to be used as the silane graft-modifiedpolyolefin may be one with a viscosity-average molecular weight (Mv) of100,000 to 1,000,000, a weight-average molecular weight (Mw) of 30,000to 920,000, and a number-average molecular weight of 10,000 to 150,000,and it may be propylene or a butene-copolymerized α-olefin. After meltkneading the polyethylene starting material with an extruder whileadding an organic peroxide (di-t-butyl peroxide) and generating radicalsin the polymer chain of the α-olefin, it was filled withtrimethoxyalkoxide-substituted vinylsilane and addition reaction wascarried out to introduce alkoxysilyl groups into the α-olefin polymer,forming a silane-graft structure. A suitable amount of an antioxidant(pentaerythritoltetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate])was simultaneously added to adjust the radical concentration in thesystem, thus inhibiting chain-style chain reaction (gelation) in theα-olefin. The obtained silane-grafted polyolefin molten resin was cooledin water and pelletized, after which it was heat-dried at 80° C. for 2days and the water and unreacted trimethoxyalkoxide-substitutedvinylsilane were removed. The residual concentration of the unreactedtrimethoxyalkoxide-substituted vinylsilane in the pellets was about 10to 1500 ppm.

Tables 1 to 3 show silane graft-modified polyethylenes obtained by thismethod, as “Silane-modified polyethylene (B)”.

[Membrane Formation Example I] (Sheet-Forming Step)

To 79.2 weight % of polyethylene homopolymer with a weight-averagemolecular weight of 2,000,000 (polyethylene(A)) there was added 19.8weight % of silane-grafted polyethylene (silane-modified polyethylene(B)) with an MFR of 0.4 g/min, obtained using a polyolefin with aviscosity-average molecular weight of 20,000 as starting material andmodification reaction with trimethoxyalkoxide-substituted vinylsilane(the respective contents of resin compositions (A) and (B) thus being0.8 and 0.2), and 1 weight % ofpentaerythrityl-tetrakis-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionatelas an antioxidant, and these were dry blended using a tumbler blender toobtain a mixture. The obtained mixture was supplied to a twin-screwextruder through a feeder, under a nitrogen atmosphere. Liquid paraffin(kinematic viscosity at 37.78° C.: 7.59×10⁻⁵ m²/s) was also injectedinto the extruder cylinder by a plunger pump.

The mixture was melt kneaded with liquid paraffin in an extruder, andadjusted with a feeder and pump so that the quantity ratio of liquidparaffin in the extruded polyolefin composition was 70 weight % (i.e. apolymer concentration of 30 weight %). The melt kneading conditions werea preset temperature of 230° C., a screw rotational speed of 240 rpm anda discharge throughput of 18 kg/h.

The melt kneaded mixture was then extrusion cast through a T-die onto acooling roll controlled to a surface temperature of 25° C., to obtain agel sheet (molded sheet) with a raw membrane thickness of 1400 μm.

(Stretching step)

The gel sheet was then simultaneously fed into a biaxial tenterstretching machine for biaxial stretching, to obtain a stretched sheet.The stretching conditions were an MD factor of 7.0, a TD factor of 6.0(i.e. a factor of 7×6), and a biaxial stretching temperature of 125° C.

(Porous body-forming step)

The stretched gel sheet was subsequently fed into a methyl ethyl ketonetank and thoroughly immersed in the methyl ethyl ketone for extractionremoval of the liquid paraffin, after which the methyl ethyl ketone wasdried off to obtain a porous body.

(Heat treatment step)

The porous body to be subjected to heat setting (HS) was fed to a TDtenter and HS was carried out at a heat setting temperature of 125° C.and a stretch ratio of 1.8, after which relaxation was carried out to afactor of 0.5 in the TD direction (i.e. the HS relaxation factor was0.5).

(Affinity Treatment Step)

The heat-treated porous body was also fed to an ethanol bath (affinitytreatment tank) and immersed and retained for 60 seconds for affinitytreatment of the heat-treated porous body, to obtain an affinity-treatedporous body.

(Crosslinking step)

The affinity-treated porous body was further fed to a 25% aqueouscaustic soda solution (crosslinking treatment tank) and immersed andretained for 60 seconds for crosslinking treatment of theaffinity-treated porous body to obtain a crosslinked porous body.

(Washing and drying step)

The crosslinked porous body was fed into water (washing treatment tank)and immersed and retained for 60 seconds for washing of the crosslinkedporous body. It was then fed to a conveyor dryer and dried at 120° C.for 60 seconds to obtain a microporous membrane.

The obtained microporous membrane was then cut at the edges and wound upas a mother roll with a width of 1,100 mm and a length of 5,000 m.

Examples I-1 to I-11 and Comparative Examples I-1 to I-4

The microporous membranes listed in Tables 1 to 3 were obtained by thesame procedure as Membrane Formation Example I, except for changing thequantity ratio of components A and B and the crosslinking method andconditions as shown in Tables 1 to 3. The obtained microporous membraneswere subjected to each evaluation by the evaluation methods describedabove, and the evaluation results are shown in Tables 1 to 3.

A TMA graph (FIG. 1 ), a heat release graph (FIG. 2 ) and voltagereduction graph (FIG. 3 ) during a battery nail penetration safety testwere prepared for the separator obtained in Example I-1.

TABLE 1 Example I 1 2 3 4 5 6 Resin Polyethylene (A) 0.8 0.62 0.94 0.80.97 0.58 composition Silane-modified 0.2 0.38 0.06 0.2 0.03 0.42polyethylene (B) Kneading temperature ° C. 220 220 220 220 220 220Crosslinking Method Alkali Alkali Alkali Acid Alkali Alkali methodtreatment treatment treatment treatment treatment treatment Crosslinkingreaction timing Crosslinking Crosslinking Crosslinking CrosslinkingCrosslinking Crosslinking step step step step step step Reagent AqueousAqueous Aqueous Aqueous Aqueous Aqueous NaOH NaOH NaOH NaOH NaOH NaOHsolution solution solution solution solution solution Temperature ° C.80 80 80 60 80 80 Crosslinking treatment tank pH 14 14 14 1 14 14Washing treatment tank pH 7 - 12 7 - 12 7 - 12 3-7 7 - 12 7 - 12 BasicMembrane thickness μm 8 8 8 8 8 8 separator Porosity % 35.4 35.3 35.7 3635.3 35.3 properties Air permeability sec/100 cm³ 150 143 155 152 143143 Metal [Sn] ppm 0.1 0.1 0.1 0.1 0.1 0.1 content [Zn] ppm 0.1 0.1 0.10.1 0.1 0.1 ICP [Ti] ppm 0.5 0.5 0.5 0.5 0.5 0.5 [Cu] ppm 0.1 0.1 0.10.1 0.1 0.1 Resin aggregates in separator /1000 m² 6 12 3 5 12 283 TMAmembrane rupture temperature ° C. 207 207 207 210 160 nd Battery cyclestability 1 % 96 95 95 92 93 83 Battery Internal ° C./sec 10 11 10 12 2511 destruction maximum heat safety 1 release rate Voltage sec none nonenone none 3 none reduction (3 V reduction time) Extrusion stability A AA A A A

TABLE 2 Example I 7 8 9 10 11 Resin Polyethylene (A) 0.8 0.8 0.8 0.8 0.8composition Silane-modified polyethylene (B) 0.2 0.2 0.2 0.2 0.2Kneading temperature °C 220 220 220 220 220 Crosslinking Method AlkaliAlkali Alkali Alkali Alkali method treatment treatment treatmenttreatment treatment Crosslinking reaction timing CrosslinkingCrosslinking Crosslinking Crosslinking Crosslinking step step step stepstep Reagent Aqueous Aqueous Aqueous Aqueous Aqueous NaOH NaOH NaOH NaOHNaOH solution solution solution solution solution Temperature ° C. 80 1550 110 80 Crosslinking treatment tank pH 14 14 14 14 14 Washingtreatment tank pH 7-12 7-12 7-12 7-12 7-12 Basic separator Membranethickness μm 25 8 8 8 8 properties Porosity % 35 35.2 35.3 35.8 37 Airpermeability sec/100 cm³ 90 144 145 148 151 Metal [Sn] ppm 0.1 0.1 0.10.1 0.02 content [Zn] ppm 0.1 0.1 0.1 0.1 0.01 ICP [Ti] ppm 0.5 0.5 0.50.5 0.01 [Cu] ppm 0.1 0.1 0.1 0.1 0.05 Resin aggregates in separator/1000 m² 7 5 5 7 6 TMA membrane rupture temperature ° C. 207 155 178 230182 Battery cycle stability 1 % 80 80 83 88 78 Battery destructionInternal ° C./sec 7 25 30 35 10 safety 1 maximum heat release rateVoltage sec none 6 5 5 none reduction (3 V reduction time) Extrusionstability A A A A A

TABLE 3 Comparative Example I 1 2 3 4 Resin composition Polyethylene (A)0 0.8 0.8 0.8 Silane-modified polyethylene (B) 1.0 0.2 0.2 0.2 Kneadingtemperature ° C. 220 220 220 220 Crosslinking Method Alkali treatmentHot water Dehydrating Dehydrating method treatment condensationcondensation catalyst catalyst Crosslinking reaction timing Crosslinkingstep Crosslinking step Sheet-forming Porous body-forming Reagent AqueousNaOH Steam step step solution Temperature ° C. 80 90 220 85 Crosslinkingtreatment tank pH 14 7 — — Washing treatment tank pH 7 to 12 7 — — Basicseparator Membrane thickness μm 8 8 8.2 8 properties Porosity % 35 35 336 Air permeability sec/100 cm³ 3600 147 9050 155 Metal [Sn] ppm 0.1 0.1310 220 content [Zn] ppm 0.1 0.1 0.1 0.1 ICP [Ti] ppm 0.5 0.5 0.5 0.5[Cu] ppm 0.1 0.1 0.1 0.1 Resin aggregates in separator /1000 m² 2902 53287 5 TMA membrane rupture temperature ° C. 207 135 175 178 Batterycycle stability 1 % — 90 — 55 Battery destruction Internal ° C./sec 18 —— 14 safety 1 maximum heat release rate Voltage reduction sec 6 2 — none(3 V reduction time) Extrusion stability A A B A

The term “resin composition” used in Tables 1 to 3 indicates thepercentage with respect to the total silane graft-modified polyolefinand polyethylene content.

The term “method” used in Tables 1 to 3 indicates the method of thesilane crosslinking reaction, classifying it as an alkali treatment,acid treatment, hot water treatment or dehydrating condensation catalystmethod.

The term “timing of crosslinking reaction” used in Tables 1 to 3indicates that the silane crosslinking reaction was carried out in the(1) sheet-forming step, (2) stretching step, (3) porous body-formingstep, (4) heat treatment step, (5) affinity treatment step, (6)crosslinking step or (7) washing and drying step as described above.

Incidentally, in Example 1-4a 10% hydrochloric acid solution was usedinstead of a 25% aqueous caustic soda solution, and in ComparativeExample 1-2 the crosslinking step of the Membrane Formation Example wascarried out using a 2.5 kg/m² steam treatment tank instead of immersionin a 25% aqueous caustic soda solution. For Comparative Examples 1-3 and1-4, crosslinking reaction was carried out with the timing listed inTable 3, and the crosslinking step was omitted.

In Example I-11, the washing time in the production example describedabove was changed from 60 seconds to 10 minutes for adjustment of theamount of metal ion.

The term “reagent” in Tables 1 to 3 indicates the reagent used for thecrosslinking step in the Membrane Formation Example, with the exceptionof Comparative Examples 1-3 and 1-4.

The term “temperature” in Tables 1 to 3 indicates the temperature duringthe step listed under “Timing of crosslinking reaction”.

The terms “crosslinking treatment tank pH” and “washing treatment tankpH” in Tables 1 to 3 indicate the pH values in each tank, and forexample, “7 to 12” means that the pH was distributed across a range fromthe area near the tank inlet to the area near the outlet.

The “silane-modified polyethylene (B)” in Tables 1 to 3 is asilane-modified polyethylene with a density of 0.95 g/cm³ and a meltmass-flow rate (MFR) of 0.4 g/min at 190° C.

<Experiment Group II> [Silane Graft-Modified Polyolefin ProductionMethod]

The polyolefin starting material to be used as the silane graft-modifiedpolyolefin may be one with a viscosity-average molecular weight (Mv) of100,000 to 1,000,000, a weight-average molecular weight (Mw) of 30,000to 920,000, and a number-average molecular weight of 10,000 to 150,000,and it may be propylene or a butene-copolymerized α-olefin. After meltkneading the polyethylene starting material with an extruder whileadding an organic peroxide (di-t-butyl peroxide) and generating radicalsin the polymer chain of the α-olefin, it was filled withtrimethoxyalkoxide-substituted vinylsilane and addition reaction wascarried out to introduce alkoxysilyl groups into the α-olefin polymer,forming a silane-graft structure. A suitable amount of an antioxidant(pentaerythritoltetrakis[3-(3,5-di-tetra-butyl-4-hydroxyphenyl)propionate])was simultaneously added to adjust the radical concentration in thesystem, thus inhibiting chain-style chain reaction (gelation) in theα-olefin. The obtained silane-grafted polyolefin molten resin was cooledin water and pelletized, after which it was heat-dried at 80° C. for 2days and the water and unreacted trimethoxyalkoxide-substitutedvinylsilane were removed. The residual concentration of the unreactedtrimethoxyalkoxide-substituted vinylsilane in the pellets was about 10to 1500 ppm.

The silane graft-modified polyolefins obtained by this method was usedas the “Silane-modified polyethylene (B)” in Tables 1 to 3. The silanegraft-modified polyolefin used here had a density of 0.94 g/cm³ and anMFR of 0.65 g/min.

[Membrane Formation and Coating Example II] (Formation of MicroporousMembrane)

To 79.2 wt % of polyethylene homopolymer with a weight-average molecularweight of 500,000 (polyethylene (A)) there was added 19.8 wt % ofsilane-grafted polyethylene (silane-modified polyethylene (B)) with anMFR (190° C.) of 0.4 g/min, obtained using a polyolefin with aviscosity-average molecular weight of 20,000 as starting material andmodification reaction with trimethoxyalkoxide-substituted vinylsilane(the respective contents of resin compositions (A) and (B) thus being80% and 20%), and 1 wt % ofpentaerythrityl-tetrakis-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionatelas an antioxidant, and these were dry blended using a tumbler blender toobtain a mixture. The obtained mixture was supplied to a twin-screwextruder through a feeder, under a nitrogen atmosphere. Liquid paraffin(kinematic viscosity at 37.78° C.: 7.59×10⁻⁵ m²/s) was also injectedinto the extruder cylinder by a plunger pump.

The mixture was melt kneaded with liquid paraffin in an extruder, andadjusted with a feeder and pump so that the quantity ratio of liquidparaffin in the extruded polyolefin composition was 70 wt % (i.e. apolymer concentration of 30 wt %). The melt kneading conditions were apreset temperature of 220° C., a screw rotational speed of 240 rpm and adischarge throughput of 18 kg/h.

The melt kneaded mixture was then extrusion cast through a T-die onto acooling roll controlled to a surface temperature of 25° C., to obtain agel sheet (molded sheet) with a raw membrane thickness of 1400 μm.

The molded sheet was then simultaneously fed into a biaxial tenterstretching machine for biaxial stretching, to obtain a stretched sheet.The stretching conditions were an MD factor of 7.0, a TD factor of 6.0(i.e. a factor of 7×6), and a biaxial stretching temperature of 125° C.

The stretched gel sheet was subsequently fed into a methyl ethyl ketonetank and thoroughly immersed in the methyl ethyl ketone for extractionremoval of the liquid paraffin, after which the methyl ethyl ketone wasdried off to obtain a porous body.

The porous body to be subjected to heat setting (HS) was fed to a TDtenter and HS was carried out at a heat setting temperature of 125° C.and a stretch ratio of 1.8, after which relaxation was carried out to afactor of 0.5 in the TD direction (i.e. the HS relaxation factor was0.5), to obtain a microporous membrane.

The obtained microporous membrane was then cut at the edges and wound upas a microporous membrane mother roll with a width of 1,100 mm and alength of 5,000 m.

(Method for Producing Acrylic Latex)

The acrylic latex to be used as the resin binder is produced by thefollowing method.

Into a reactor equipped with a stirrer, reflux condenser, drip tank andthermometer there were loaded 70.4 parts by weight of ion-exchangedwater, 0.5 part by weight of “AQUALON KH1025” (registered trademark ofDai-ichi Kogyo Seiyaku Co., Ltd., 25% aqueous solution) as anemulsifier, and 0.5 part by weight of “ADEKA REASOAP SR1025” (registeredtrademark of Adeka Corp., 25% aqueous solution). The internaltemperature of the reactor was then raised to 80° C., and 7.5 parts byweight of a 2% aqueous solution of ammonium persulfate was added whilekeeping the temperature at 80° C., to obtain an initial mixture. Fiveminutes after addition of the ammonium persulfate aqueous solution wascompleted, the emulsified liquid was added dropwise from the drip tankinto the reactor over a period of 150 minutes.

The emulsified liquid was prepared by forming a mixture of 70 parts byweight of butyl acrylate; 29 parts by weight of methyl methacrylate; 1part by weight of methacrylic acid; 3 parts by weight of “AQUALONKH1025” (registered trademark of Dai-ichi Kogyo Seiyaku Co., Ltd., 25%aqueous solution) and 3 parts by weight “ADEKA REASOAP SR1025”(registered trademark of Adeka Corp., 25% aqueous solution) asemulsifiers; 7.5 parts by weight of a 2% aqueous solution of ammoniumpersulfate; and 52 parts by weight of ion-exchanged water, and mixingwith a homomixer for 5 minutes.

Upon completion of the dropwise addition of the emulsified liquid, theinternal temperature of the reactor was kept at 80° C. for a period of90 minutes, after which it was cooled to room temperature. The obtainedemulsion was adjusted to a pH of 8.0 with a 25% aqueous ammoniumhydroxide solution, and then a small amount of water was added to obtainan acrylic latex with a solid content of 40%. The obtained acrylic latexhad a number-mean particle size of 145 nm and a glass transitiontemperature of −23° C.

(Formation of Inorganic Porous Layer)

A dispersion was prepared by evenly dispersing 95 parts by weight ofaluminum hydroxide oxide (mean particle size: 1.4 μm as inorganicparticles and 0.4 part by (solid) weight of an aqueous ammoniumpolycarboxylate solution (SN dispersant 5468 by San Nopco, Ltd., 40%solid concentration) as an ionic dispersing agent, in 100 parts byweight of water. The obtained dispersion was shredded with a bead mill(cell volume: 200 cc, zirconia bead diameter: 0.1 mm, filling volume:80%), and the particle size distribution of the inorganic particles wasadjusted to D50=1.0 μm. To the particle size distribution-adjusteddispersion there was added 4.6 parts by (solid) weight of an acryliclatex (solid concentration: 40%, mean particle size: 145 nm, glasstransition temperature: −23° C., constituent monomers: butyl acrylate,methyl methacrylate, methacrylic acid) as a resin binder to prepare aninorganic particle-containing slurry.

The microporous membrane was then continuously wound out from themicroporous membrane mother roll and one side of the microporousmembrane was coated with the inorganic particle-containing slurry usinga gravure reverse coater, after which it was dried with a dryer at 60°C. to remove the water and wound up to obtain a separator mother roll.

During the evaluation, the separator wound out from the mother roll wasslit as necessary for use as the evaluation separator.

[Examples II-1 to 11-2 and Comparative Example II-21

The microporous membranes listed in Tables 1 to 3 were obtained by thesame procedure as Membrane Formation and Coating Example II, except forchanging the quantity ratio of components A and B, the presence orabsence of the inorganic layer and the crosslinking method andconditions, as shown in Tables 1 to 3.

In Example II-1 the microporous membrane was fed into a 25% aqueouscaustic soda solution (temperature: 80° C., pH 8.5 to 14) and in Example11-2 it was fed into an aqueous 10% hydrochloric acid solution(temperature: 60° C., pH 1 to 6.5), and immersed and retained for 60seconds for crosslinking treatment of the microporous membrane, beforeforming the inorganic porous layer.

Comparative Example II-1

To 79.2 wt % of polyethylene homopolymer with a weight-average molecularweight of 500,000 (polyethylene(A)) there was added 19.8 wt % ofsilane-grafted polyethylene (silane-modified polyethylene (B)) with anMFR (190° C.) of 0.4 g/min, obtained using a polyolefin with aviscosity-average molecular weight of 20,000 as starting material andmodification reaction with trimethoxyalkoxide-substituted vinylsilane(the respective contents of resin compositions (A) and (B) thus being80% and 20%), and 1 wt % ofpentaerythrityl-tetrakis-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionatelas an antioxidant, and these were dry blended using a tumbler blender toobtain a mixture. The obtained mixture was supplied to a twin-screwextruder through a feeder, under a nitrogen atmosphere. Liquid paraffin(kinematic viscosity at 37.78° C.: 7.59×10⁻⁵ m²/s) was also injectedinto the extruder cylinder by a plunger pump.

The mixture was melt kneaded with liquid paraffin in an extruder, andadjusted with a feeder and pump so that the quantity ratio of liquidparaffin in the extruded polyolefin composition was 70 wt % (i.e. apolymer concentration of 30 wt %). The melt kneading conditions were apreset temperature of 220° C., a screw rotational speed of 240 rpm and adischarge throughput of 18 kg/h.

The melt kneaded mixture was then extrusion cast through a T-die onto acooling roll controlled to a surface temperature of 25° C., to obtain agel sheet (molded sheet) with a raw membrane thickness of 1400 μm.

The molded sheet was then simultaneously fed into a biaxial tenterstretching machine for biaxial stretching, to obtain a stretched sheet.The stretching conditions were an MD factor of 7.0, a TD factor of 6.0(i.e. a factor of 7×6), and a biaxial stretching temperature of 125° C.

The stretched gel sheet was subsequently fed into a methyl ethyl ketonetank and thoroughly immersed in the methyl ethyl ketone for extractionremoval of the liquid paraffin, after which the methyl ethyl ketone wasdried off to obtain a porous body.

The porous body to be subjected to heat setting (HS) was fed to a TDtenter and HS was carried out at a heat setting temperature of 125° C.and a stretch ratio of 1.8, after which relaxation was carried out to afactor of 0.5 in the TD direction (i.e. the HS relaxation factor was0.5).

In Comparative Example 1, the heat-treated porous body was to be used asthe separator, and therefore the obtained porous body was cut at theedges and wound up as a mother roll with a width of 1,100 mm and alength of 5,000 m.

The obtained heat-treated porous body was also fed into an ethanol bath(affinity treatment tank) and immersed and retained for 60 seconds foraffinity treatment of the heat-treated porous body to obtain anaffinity-treated porous body.

In addition, the affinity-treated porous body was fed into a 25% aqueouscaustic soda solution (temperature: 80° C., pH 8.5 to 14) and immersedand retained for 60 seconds for crosslinking treatment of theaffinity-treated porous body to obtain a crosslinked porous body.

The crosslinked porous body was fed into water (washing treatment tank)and immersed and retained for 60 seconds for washing of the crosslinkedporous body. It was then fed to a conveyor dryer and dried at 120° C.for 60 seconds to obtain a microporous membrane.

The obtained microporous membrane was cut at the edges and wound up as amother roll with a width of 1,100 mm and a length of 5,000 m.

During the evaluation for Comparative Example II-1, the microporousmembrane wound out from the mother roll was slit as necessary for use asthe evaluation separator.

[Evaluation Results]

The microporous membranes and batteries obtained in Examples II-1 to11-2 and Comparative Examples II-1 to 11-2 were evaluated by each of theevaluation methods described above, and the evaluation results are shownin Table 4.

TABLE 4 Comparative Comparative Example II-1 Example 11-2 Example II-1Example 11-2 Separator Resin composition Polyethylene (A) wt % 80% 80%80% 100% Silane-modified wt % 20% 20% 20%   0% polyethylene(B) Kneadingtemperature ° C. 220 220 220 220 Inorganic layer Inorganic particlesWeight ratio 95% 95% — 95% composition Type AlO(OH) AlO(OH) AlO(OH)Resin binder Tg(° C.) -23 -23 −23 Crosslinking Method Alkali treatmentAcid treatment Alkali treatment — method Crosslinking reaction tintingAfter pore After pore After pore formation formation formation ReagentNaOHaq HClaq NaOHaq Temperature ° C. 80 60 80 pH 8.5-14 1-6.5 8.5- 14Basic properties Membrane thickness μm 11 11 11 9.5 of resinous Porosity% 40 40 40 38 microporous membrane Air permeability sec/100 cm³ 160 160160 172 Inorganic layer thickness μm 4 4 — 4 Shutdown/ Shutdowntemperature (i) ° C. 165 171 165 143 rupture resistance Membrane rupture° C. >200 >200 >200 151 temperature (i) Resin aggregates in microporousmembrane /1000 m² 2 2 2 3 Battery Crosslinking method — — — — Batterycycle stability 1 % 97 97 54 96 Battery destruction Internal maximum °C./sec 6 6 120 235 safety 1 heat release rate Voltage reductionsec >300 >300 7 2 (3 V reduction time)

Experiment Group III Example III-1 Fabrication of Layer a (Fabricationof Silane Graft-Modified Polyolefin)

Using polyethylene with a viscosity-average molecular weight of 100,000as the polyethylene, the polyethylene starting material was melt kneadedwith an extruder while adding an organic peroxide (di-t-butyl peroxide)and generating radicals in the polymer chain of the α-olefin, and thenit was filled with trimethoxyalkoxide-substituted vinylsilane andaddition reaction was carried out to introduce alkoxysilyl groups intothe α-olefin polymer, forming a silane-graft structure. A suitableamount of an antioxidant(pentaerythritoltetrakis[3-(3,5-di-tetra-butyl-4-hydroxyphenyl)propionate])was simultaneously added to the reaction system to adjust the radicalconcentration in the system, thus inhibiting chain-style chain reaction(gelation) in the α-olefin. The obtained silane-grafted polyolefinmolten resin was cooled in water and pelletized, after which it was heatdried at 80° C. for 2 days and the water and unreactedtrimethoxyalkoxide-substituted vinylsilane were removed. The residualconcentration of the unreacted trimethoxyalkoxide-substitutedvinylsilane in the pellets was about 1500 ppm or lower.

Modification reaction of the trimethoxyalkoxide-substituted vinylsilanein this manner yielded a silane-modified polyethylene with an MFR (190°C.) of 0.4 g/min.

(Fabrication of Layer A)

After combining 35 weight % of the previously obtained silane-modifiedpolyethylene with 65 weight % of polyethylene homopolymer having aweight-average molecular weight of 700,000 to obtain a resin blend, 1weight % ofpentaerythrityl-tetrakis-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionatelwas added to the blend as an antioxidant, and a tumbler blender was usedfor dry blending to obtain a mixture. The obtained mixture was suppliedto a twin-screw extruder through a feeder, under a nitrogen atmosphere.Liquid paraffin (kinematic viscosity at 37.78° C.: 7.59×10⁻⁵ m²/s) wasalso injected into the extruder cylinder by a plunger pump.

The mixture was melt kneaded with liquid paraffin in an extruder, andadjusted with a feeder and pump so that the quantity ratio of liquidparaffin in the extruded polyolefin composition was 70 weight % (i.e. apolymer concentration of 30 weight %). The melt kneading conditions werea preset temperature of 220° C., a screw rotational speed of 240 rpm anda discharge throughput of 18 kg/h. The melt kneaded mixture wasextrusion cast through a T-die onto a cooling roll controlled to asurface temperature of 25° C., to obtain a gel sheet (molded sheet) witha raw membrane thickness of 1400 μm.

The molded sheet was then simultaneously fed into a biaxial tenterstretching machine for biaxial stretching, to obtain a stretched sheet.The stretching conditions were an MD factor of 7.0, a TD factor of 6.0(i.e. a factor of 7×6), and a biaxial stretching temperature of 123° C.

The stretched gel sheet was fed into a dichloromethane tank andthoroughly immersed in the dichloromethane for extraction removal of theliquid paraffin, after which the dichloromethane was dried off to obtaina porous body.

Next, the porous body to be subjected to heat setting (HS) was fed to aTD tenter for heat setting and relaxation. The heat setting conditionsinputted to the TD tenter were for HS at a heat setting temperature of132° C. and a stretch ratio of 2.1, and this was followed by relaxationto a TD factor of 1.9 to obtain a microporous membrane.

The obtained microporous membrane was then cut at the edges and wound upas a mother roll with a width of 1,100 mm and a length of 5,000 m.

During the evaluation, the microporous membrane wound out from themother roll was slit as necessary for use as the evaluation layer A.

The membrane thickness, air permeability and porosity were measured forthe obtained evaluation layer A, and they are shown in Table 5.

<Fabrication of Layer B>

A dispersion was prepared by evenly dispersing 95 parts by weight ofaluminum hydroxide oxide (mean particle size: 1.4 μm as inorganicparticles and 0.4 part by (solid) weight of an aqueous ammoniumpolycarboxylate solution (SN dispersant 5468 by San Nopco, Ltd., 40%solid concentration) as an ionic dispersing agent, in 100 parts byweight of water. The obtained dispersion was shredded with a bead mill(cell volume: 200 cc, zirconia bead diameter: 0.1 mm, filling volume:80%), and the particle size distribution of the inorganic particles wasadjusted to D50=1.0 μm, to prepare an inorganic particle-containingslurry.

The microporous membrane was then continuously wound out from themicroporous membrane mother roll and one side of the microporousmembrane was coated with the inorganic particle-containing slurry usinga gravure reverse coater, after which it was dried with a dryer at 60°C. to remove the water and wound up to obtain a separator mother roll.

During the evaluation, the separator was wound out from the mother rolland slit as necessary for use as the evaluation separator.

[Examples 111-2 to III-14 and Comparative Examples III-1 and 111-21

With the physical properties listed in Table 5 as the target, one ormore from among the weight-average molecular weight of the polyethylenehomopolymer, the set stretching conditions, the heat setting conditionsand the relaxation conditions were changed. The composition of layer Bwas also changed as shown in Table 5.

Separators were fabricated by the same method as Example III-1 exceptfor these changes, and the obtained separators were used for theevaluation described above. The evaluation results are shown in Table 5.

TABLE 5 Example III 1 2 3 4 5 6 7 8 Separtor Layer A Polyethylene weight65 65 65 65 65 65 60 95 % Silane-modified weight 35 35 35 35 35 35 40 5polyolefin % Thickness (TA) μm 11.0 3.0 20.5 3.0 11.0 11.0 11.0 11.0Porosity % 45 38 49 38 45 45 38 42 Air permeability sec/cm³ 112 105 126105 112 112 152 107 Puncture strength gf/20 μm 510 380 560 1192 510 510506 505 Layer B Inorganic Weight wt % 95.00 95.00 95.00 95.00 95.0095.00 98.00 35.00 particles ratio — AlO AlO AlO AlO AlO AlO AlO AlO Type(OH) (OH) (OH) (OH) (OH) (OH) (OH) (OH) Thickness (TB) μm 3.5 12 1.5 13.5 3.5 3.5 3.5 Ratio (TA/TB) — 3.14 0.25 13.67 3.00 3.14 3.14 3.14 3.14Total thickness (TA + TB) μm 14.5 15 22 4 14.5 14.5 14.5 14.5 TMA testMembrane ° C. 210.00 212.00 208.00 210.00 175.00 225.00 211.00 207.00rupture temperature F/MD test Shutdown ° C. 143 142 144 142 131 160 143143 temperature (ii) Meltdown ° C. 220 210 230 200 205 200 203 210temperature (ii) 150° Before % 56 55 63 53 57 57 58 55 Cheat formationof crosslinked structure shrinkage After % 7 4 11 9 5 7 2 48 formationof crosslinked structure factor Change factor factor 0.13 0.07 0.17 0.170.13 0.13 0.03 0.87 Battery Battery cycle stability 2 % 98 98 98 98 9798 93 93 (300 cycles) Passing 200 cycles % 97 95 95 97 95 97 97 97 ratetest 2 in safety 1000 cycles % 90 89 87 88 88 89 81 83 ComparativeExample III Example III 9 10 11 12 13 14 1 2 Separtor Layer APolyethylene weight 65 65 40 65 65 60 65 65 % Silane-modified weight 3535 60 35 35 40 35 35 polyolefin % Thickness (TA) μm 20.0 3.0 3.0 11.0 59.0 11.5 3.0 Porosity % 45 45 38 45 36 40 45 46 Air permeability sec/cm³112 112 105 112 150 90 112 112 Puncture strength gf/20 μm 510 510 380510 250 250 1168 1168.5 Layer B Inorganic Weight wt % 95.00 95.00 94.0099.50 95 98 95.00 94.00 particles ratio — AlO AlO AlO AlO AlO AlO AlOAlO Type (OH) (OH) (OH) (OH) (OH) (OH) (OH) (OH) Thickness (TB) μm 3.50.5 12 3.5 0.4 3 0.5 16 Ratio (TA/TB) — 5.71 6.00 0.25 3.14 12.5 0.3323.00 0.19 Total thickness (TA + TB) μm 23.5 3.5 15 14.5 5.4 12 12.0019.00 TMA test Membrane ° C. 215.00 205.00 211.00 209.00 198 208 178.00159.00 rupture temperature F/MD test Shutdown ° C. 143 143 140 143 143136.5 140 142 temperature (ii) Meltdown ° C. 210 215 215 200 220 >200175 156 temperature (ii) 150° Before % 56 56 63 56 51 55 63 53 Cheatformation of crosslinked structure shrinkage After % 7 7 1.2 7 3 4 1.249 formation of crosslinked structure factor Change factor factor 0.130.13 0.02 0.13 0.06 0.07 0.019 0.92 Battery Battery cycle stability 2 %89 91 81 65 91 95 65 60 (300 cycles) Passing 200 cycles % 95 96 83 97 9392 48 43 rate test 2 in safety 1000 cycles % 78 73 60 63 81 87 0 0

Experiment Group IV Example IV-1 Fabrication of Layer a Fabrication ofSilane Graft-Modified Polyolefin

Using polyethylene with a viscosity-average molecular weight of 100,000as the polyethylene, the polyethylene starting material was melt kneadedwith an extruder while adding an organic peroxide (di-t-butyl peroxide)and generating radicals in the polymer chain of the α-olefin, and thenit was filled with trimethoxyalkoxide-substituted vinylsilane andaddition reaction was carried out to introduce alkoxysilyl groups intothe α-olefin polymer, forming a silane-graft structure. A suitableamount of an antioxidant(pentaerythritoltetrakis[3-(3,5-di-tetra-butyl-4-hydroxyphenyl)propionate])was simultaneously added to the reaction system to adjust the radicalconcentration in the system, thus inhibiting chain-style chain reaction(gelation) in the α-olefin. The obtained silane-grafted polyolefinmolten resin was cooled in water and pelletized, after which it washeat-dried at 80° C. for 2 days and the water and unreactedtrimethoxyalkoxide-substituted vinylsilane were removed. The residualconcentration of the unreacted trimethoxyalkoxide-substitutedvinylsilane in the pellets was about 1500 ppm or lower.

Modification reaction of the trimethoxyalkoxide-substituted vinylsilanein this manner yielded a silane-modified polyethylene with an MFR (190°C.) of 0.4 g/min.

(Fabrication of Layer A)

After combining 35 weight % of the previously obtained silane-modifiedpolyethylene with 65 weight % of polyethylene homopolymer having aweight-average molecular weight of 750,000 to obtain a resin blend, 1weight % ofpentaerythrityl-tetrakis-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionatelwas added to the blend as an antioxidant, and a tumbler blender was usedfor dry blending to obtain a mixture. The obtained mixture was suppliedto a twin-screw extruder through a feeder, under a nitrogen atmosphere.Also, liquid paraffin (kinematic viscosity at 37.78° C.: 7.59×10⁻⁵ m²/s)was injected into the extruder cylinder by a plunger pump.

The mixture was melt kneaded with liquid paraffin in an extruder, andadjusted with a feeder and pump so that the quantity ratio of liquidparaffin in the extruded polyolefin composition was 70 weight % (i.e. apolymer concentration of 30 weight %). The melt kneading conditions werea preset temperature of 220° C., a screw rotational speed of 240 rpm anda discharge throughput of 18 kg/h. The melt kneaded mixture was thenextrusion cast through a T-die onto a cooling roll controlled to asurface temperature of 25° C., to obtain a gel sheet (molded sheet) witha raw membrane thickness of 1280 μm.

The molded sheet was then simultaneously fed into a biaxial tenterstretching machine for biaxial stretching, to obtain a stretched sheet.The stretching conditions were an MD factor of 7.0, a TD factor of 6.5(i.e. a factor of 7×6.5), and a biaxial stretching temperature of 125°C.

The stretched gel sheet was fed into a dichloromethane tank andthoroughly immersed in the dichloromethane for extraction removal of theliquid paraffin, after which the dichloromethane was dried off to obtaina porous body.

The porous body to be subjected to heat setting (HS) was fed to a TDtenter and HS was carried out at a heat setting temperature of 131° C.and a stretch ratio of 1.9, after which relaxation was carried out to afactor of 1.7 in the TD direction to obtain a microporous membrane.

The obtained microporous membrane was then cut at the edges and wound upas a mother roll with a width of 1,100 mm and a length of 5,000 m.

During the evaluation, the microporous membrane wound out from themother roll was slit as necessary for use as the evaluation layer A.

The membrane thickness, air permeability and porosity were measured forthe obtained evaluation layer A, and they are shown in Table 6.

<Fabrication of Layer B>

A dispersion was prepared by evenly dispersing 95 parts by weight ofaluminum hydroxide oxide (mean particle size: 1.4 μm as inorganicparticles and 0.4 part by (solid) weight of an aqueous ammoniumpolycarboxylate solution (SN dispersant 5468 by San Nopco, Ltd., 40%solid concentration) as an ionic dispersing agent, in 100 parts byweight of water. The obtained dispersion was shredded with a bead mill(cell volume: 200 cc, zirconia bead diameter: 0.1 mm, filling volume:80%), and the particle size distribution of the inorganic particles wasadjusted to D50=1.0 μm, to prepare an inorganic particle-containingslurry.

The microporous membrane was then continuously wound out from themicroporous membrane mother roll and one side of the microporousmembrane was coated with the inorganic particle-containing slurry usinga gravure reverse coater, after which it was dried with a dryer at 60°C. to remove the water and wound up to obtain a separator mother roll.

During the evaluation, the separator was wound out from the mother rolland slit as necessary for use as the evaluation separator.

[Examples IV-2 to IV-3 and Comparative Examples IV-1 to IV-21

With the physical properties listed in Table 6 as the target, one ormore from among the weight-average molecular weight of the polyethylenehomopolymer, the set stretching conditions, the heat setting conditionsand the relaxation conditions were changed. The composition of layer Bwas also changed as shown in Table 6.

Separators were fabricated by the same method as Example IV-1 except forthese changes, and the obtained separators were used for the evaluationdescribed above. The evaluation results are shown in Table 6.

TABLE 6 Example IV Comparative Example IV 1 2 3 1 2 Separator Layer APolyethylene weight % 65 65 65 65 65 Silane-modified polyolefin weight %35 35 35 35 35 Thickness (TA) μm 11.0 11.0 11.0 11.5 3.0 Porosity % 4845 45 25 45 Air permeability sec/cm³ 108 112 112 280 112 Puncturestrength gf/20 μm 420 510 510 168 168.5 Layer B Inorganic particlesWeight ratio wt % 95.00 95.00 95.00 95.00 94.00 Type — AlO(OH) AlO(OH)AlO(OH) AlO(OH) AlO(OH) Thickness (TB) μm 3.5 3.5 3.5 0.5 16 Ratio(TA/TB) — 3.14 3.14 3.14 23.00 0.19 Total thickness (TA+TB) μm 14.5 14.514.5 12.00 19.00 TMA test Membrane rupture ° C. 210.00 175.00 225.00178.00 159.00 temperature F/MD test Shutdown temperature (ii) ° C. 143131 160 128 165 Meltdown temperature (ii) ° C. 219 205 200 175 156 150°C. heat Before formation of % 56 57 57 65 38 shrinkage factorcrosslinked structure After formation of % 7 5 7 48 30 crosslinkedstructure Change factor times 0.13 0.13 0.13 0.738 0.789 Battery Batterycycle stability 2 (300 cycles) % 99 97 98 38 61 Passing rate in 200cycles % 96 95 97 38 41 safety test 2 1000 cycles % 92 88 89 3 1

<Experiment Group V>

Porous membranes were formed in the same manner as Examples 1 to 3 andComparative Examples 2 to 3 described in PTL 5 (Japanese UnexaminedPatent Publication No. 2001-176484), and were provided as porousmembranes V-1 to V-5, respectively. The gel fraction (%), heat-resistanttemperature (° C.) and needle puncture strength (gf/25 μm) of the porousmembranes V-1 to V-5 were evaluated by the methods described in PTL 5,and the TMA membrane rupture temperature under load was measuredaccording to <TMA membrane rupture temperature> of the presentspecification. The results are shown in Table 7.

TABLE 7 Needle TMA membrane Porous Gel Heat-resistant puncture rupturetemperature Membrane PTL 5 fraction temperature strength load (° C.) inpresent Example Example No. (%) (° C.) (gf/25 μm) specification V-1Example 1 68 185 450 <180 V-2 Example 2 69 205 680 <180 V-3 Example 3 42170 460 <180 V-4 Comparative 36 155 440 <180 Example 2 V-5 Comparative80 200 260 <180 Example 3

The following is clear from Table 7.

(a) Since the heat-resistant temperatures in PTL 5 are measuringtemperatures under conditions without an applied load, they do notcorrespond to the TMA membrane rupture temperature as explained for thefirst, second and third embodiments of the present invention.

(b) When the porous membranes V-1 to V-5 crosslinked under theconditions of 90° C. temperature, 95% humidity and 4 hours, as describedin Examples 1 to 3 and Comparative Examples 2 and 3 of PTL 5 aremeasured for TMA membrane rupture temperature under the conditionsdescribed in <TMA membrane rupture temperature>, their TMA membranerupture temperatures are below 180° C.

1-21. (canceled)
 22. A separator for an electricity storage devicecomprising a first porous layer (layer A) with a crosslinked structurethat includes a silane-modified polyolefin, and a second porous layer(layer B) that includes inorganic particles, wherein: the ratio of thethickness (TA) of layer A with respect to the thickness (TB) of layer B(TA/TB) is 0.22 to
 14. 23. The separator for an electricity storagedevice according to claim 22, wherein the membrane rupture temperatureof layer A is 180° C. to 220° C., as measured by thermomechanicalanalysis (TMA).
 24. The separator for an electricity storage deviceaccording to claim 22, wherein the total thickness of layer A and layerB (TA+TB) is 3.0 μm to 22 μm.
 25. The separator for an electricitystorage device according to claim 22, wherein the amount of theinorganic particles in layer B is 20 weight % to 99.5% weight % based onthe total weight of layer B.
 26. The separator for an electricitystorage device according to claim 22, wherein layer B includes a resinbinder.
 27. The separator for an electricity storage device according toclaim 22, wherein layer A further includes polyethylene as a polyolefindifferent from the silane-modified polyolefin.
 28. The separator for anelectricity storage device according to claim 22, wherein the amount ofthe silane-modified polyolefin in layer A is 3 weight % or greater basedon the total weight of layer A.
 29. A separator for an electricitystorage device wherein the shutdown temperature is 130° C. to 160° C.and the meltdown temperature is 200° C. or higher, as measured based onthe electrical resistance under pressure of 10.0 MPa.
 30. A method forproducing the separator for an electricity storage device according toclaim 22, comprising the following steps: (1) a sheet-forming step inwhich a silane-modified polyolefin, polyethylene and a plasticizer areextruded into a sheet using an extruder, cooled to solidification andshaped into a molded sheet; (2) a stretching step in which the moldedsheet is subjected to biaxial stretching to a 20-fold to 250-fold areaincrease to form a stretched sheet; (3) a porous body-forming step inwhich the plasticizer is extracted from the stretched sheet to form aporous body; (4) a heat treatment step in which the porous body issubjected to heat treatment and subjected to stretching and relaxationin the transverse direction to obtain a heat-treated porous body; (5) anaffinity treatment step in which the heat-treated porous body isimmersed in an organic solvent that is amphiphilic for water and organicmaterials, and the liquid affinity of the heat-treated porous body isincreased to obtain an affinity-treated porous body impregnated with theorganic solvent; (6) a crosslinking step in which the affinity-treatedporous body is contacted with a mixture of an organometallic catalystand water, or is immersed in a base solution or an acid solution andsubjected to silane dehydration condensation reaction to formoligosiloxane bonds, obtaining a crosslinked porous body; (7) a washingand drying step in which the crosslinked porous body is washed withwater and dried to obtain a microporous membrane comprising thesilane-modified polyolefin; and (8A) a coating step in which aninorganic porous layer including inorganic particles and a resin binderis formed on at least one surface of the microporous membrane.
 31. Anelectricity storage device comprising an electrode, the separator for anelectricity storage device according to claim 22, and a nonaqueouselectrolyte solution.